Accepted Manuscript

Synthesis, molecular structure and DFT studies of tricarbonylrhenium(I) complexes

containing nitrogen based bis, tris, tetrakis-(di-2-pyridylaminomethyl)benzene ligands

S. Sangilipandi, Dipankar Sutradhar, Werner Kaminsky, Asit K. Chandra, K. Mohan

Rao

PII: S0022-2860(16)30173-9
DOI: 10.1016/j.molstruc.2016.02.078
Reference: MOLSTR 22287

To appear in: Journal of Molecular Structure

Received Date: 10 December 2015

Revised Date: 21 February 2016
Accepted Date: 22 February 2016

Please cite this article as: S. Sangilipandi, D. Sutradhar, W. Kaminsky, A.K. Chandra, K.M. Rao,
Synthesis, molecular structure and DFT studies of tricarbonylrhenium(I) complexes containing nitrogen
based bis, tris, tetrakis-(di-2-pyridylaminomethyl)benzene ligands, Journal of Molecular Structure (2016),
doi: 10.1016/j.molstruc.2016.02.078.

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 ACCEPTED MANUSCRIPT

1 Synthesis, molecular structure and DFT studies of

2 tricarbonylrhenium(I) complexes containing nitrogen based bis, tris,

3 tetrakis-(di-2-pyridylaminomethyl)benzene ligands

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5 S. Sangilipandi a, Dipankar Sutradhar a, Werner Kaminsky b, Asit K. Chandra a,

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6 K. Mohan Rao a*

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9 Centre for Advanced Studies in Chemistry, North-Eastern Hill University,

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10 Shillong 793022, India

11 E-mail: mohanrao59@gmail.com
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12 Telephone Number: +91 364 2722620
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13 Fax Number: +91 364 2550076
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b
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15 Department of Chemistry, University of Washington, Seattle, WA 98195, USA

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17 Graphical abstract

18 A series of mononuclear tricarbonylrhenium(I) complexes containing 2,2-

19 dipyridylamine ligands have been prepared by the reaction of rhenium starting precursor with

20 various multidentate 2,2-dipyridylamine ligands in presence of toluene and they were

21 characterized by spectroscopic techniques.

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22

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24 Abstract

25 The reactions of rhenium starting precursor with the corresponding N,N-bidentate

26 2,2-dipyridylamine ligands (L1L5) in toluene medium under nitrogen atmosphere leads to

27 the formation of mononuclear tricarbonylrhenium(I) complexes. These complexes are denoted

28 by general formula fac-[Re(L)(CO)3Br] (15); where, L = 1,2-bis(di-2-

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29 pyridylaminomethyl)benzene (L1), 1,3-bis(di-2-pyridylaminomethyl)benzene (L2), 1,4-

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30 bis(di-2-pyridylaminomethyl)benzene (L3), 1,3,5-tris(di-2-pyridylaminomethyl)benzene (L4)

31 and 1,2,4,5-tetrakis(di-2-pyridylaminomethyl)benzene (L5). All these complexes have been

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32 synthesized and characterized by FT-IR, H NMR, UV-Vis and mass spectroscopic

33 techniques. Emission spectrum for these complexes has also been investigated and found that

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34 complex (5) shows maximum emission as compared to other complexes. Moreover, two of

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the complexes (2 & 4) were structurally determined by single crystal X-ray diffraction

36 analysis. The time-dependent DFT calculations were carried out for the complexes (2, 4 & 5)
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37 which show good agreement with the experimental absorption data.
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38 Keywords: tricarbonylrhenium(I) complexes, 2,2-dipyridylamine ligands, 1,3,5-tris(di-2-

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39 pyridylaminomethyl)benzene.

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41 1. Introduction

42 The photophysical and electrochemical properties of d6 transition metal containing

43 polypyridyl complexes are of more interested because of their applications in solar energy

44 conversion and molecular devices [1]. Moreover, the studies of photophysical and

45 photochemical properties of heterocyclic diimine complexes of tricarbonylrhenium(I) moieties

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46 are of great interest due to their properties similar with ruthenium(II) polypyridyl complexes in

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47 some respects [2]. Rheniumtricarbonyl polypyridyl complexes are generally highly emissive

48 luminescent materials which show long life time and are generally used as a fluorescent cell

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49 imaging, organic light emitting diodes (OLEDs) [3]. For example, the complex

50 [Re(phen)(CO)3Cl] was one of the first tricarbonylrhenium(I) diimine complexes ever

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51 synthesised and their photochemical properties has also been studied [4]. The polypyridyl like

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di-2-pyridylamine (DPA) compounds have the ability to undergo variety of interesting complex

53 formations upon binding and coordination to transition metal precursors which has already
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54 been reported [5]. The coordination chemistry of di-2-pyridylamine and its derivatives has been

55 prepared and investigated, for example, mono-, di- and tri-dpa derivatives were reported as a
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56 supramolecular compounds and luminescent materials [6-10]. Di-2-pyridylamine being an

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57 aromatic amine and it shares certain similarities to 2,2-bipyridine, however the central amine

58 unit introduces more flexibility to the pyridine rings [11]. The secondary nitrogen of each DPA
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59 unit is directly bound to an aryl core in all DPA derivative ligands. It can be noted that, in tri-

60 dpa ligand the three DPA moieties are almost perpendicular to the central trimethylenebenzene
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61 and two of them are spatially close to each other while the third one is further apart which
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62 offers certain degree of flexibility to the ligand and complexes [12].

63 Pt(II) and Pd(II) complexes of DPA derivatives have been attracted and considerably

64 used as a new class of anticancer agents that possess potent and distinct biological activity due

65 to their structural similarity to cis-platin. Moreover, several DPA derivatives of Pt(II) and

66 Pd(II) complexes have been demonstrated equally or higher antitumor activity than cis-platin,

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67 against P388 leukemia cell lines [13-17]. These complexes were forming coordination of six-

68 membered chelating rings along with the metal centre and multidentate ligands. But

69 meanwhile, bpy ligands and their derivatives are found to form coordination complexes with

70 stable five-membered chelating rings with broad range of transition metals. At the same time,

71 dpa derivative ligands found to bind to the transition metals through six-membered chelating

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72 ring formation that has not been investigated thoroughly [18].

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73 However the studies of 2,2-dipyridylamine derivative ligands (NN) containing an

74 aromatic spacer unit has not been explored much in the field of rhenium chemistry.

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75 Interestingly, the studies on Re(I)-DPA system has been carried out only on rare occasions.

76 The ligands used in this study are shown in Chart 1. In this present work, we have prepared a

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77 series of tricarbonylrhenium(I) complexes containing DPA ligands and their theoretical

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calculations were studied by using time-dependent DFT method.
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79 2. Experimental section

80 2. 1. Materials and methods

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81 All the reactions were carried out under oxygen free nitrogen atmosphere using
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82 standard Schlenk-line techniques. Starting materials were purchased from Sigma-Aldrich

83 chemicals. All solvents were dried and distilled by following the standard literature procedure
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84 [19]. Starting precursor was prepared according to literature procedure [20]. Infrared spectra

85 were recorded on a Perkin-Elmer 983 spectrometer using solid KBr pellets. 1H NMR spectra
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86 were recorded on a Bruker Avance II 400 MHz spectrometer. Mass spectra were obtained with
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87 a Waters ZQ 4000 mass spectrometer by ESI method. Absorption spectra were obtained with a

88 Perkin-Elmer Lambda 25 UV-Visible spectrophotometer at room temperature. Emission

89 spectra were recorded on a Hitachi F-4500 Fluorescence Spectrophotometer at room

90 temperature. Elemental analyses for the complexes were obtained on a Perkin-Elmer 2400

91 series II CHN/S analyzer.

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92 2. 2. Crystallographic measurements

93 Suitable single crystals of complexes (2 & 4) were grown by slow diffusion of hexane

94 over an acetone solution of the respective complex. Single crystal X-ray diffraction data for

95 complexes (2 & 4) were collected on an Oxford Diffraction Xcalibur Eos Gemini

96 diffractometer at 290-294 K using graphite monochromated Mo-K radiation ( = 0.7107 ).

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97 Data processing was undertaken with CrysAlisPro. The structures were solved by direct

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98 methods using SHELXS-97 program and refined by full matrix least-square methods with

99 SHELXL-97 refining on F2 [21]. The positions of all the atoms were obtained by direct

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100 methods. The hydrogen atoms bound to the carbon were placed in geometrically constrained

101 positions and refined with isotropic temperature factors, generally 1.2 Ueq of their parent atoms.

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102 All non-hydrogen atoms were refined anisotropically. Further details such as crystallographic

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data and structure refinement details of complexes (2 & 4) are summarized in Table 1 and

104 selected bond lengths and bond angles are listed in Table 2. Solvent molecule present in the
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105 crystal structure (2) was refined disorderedly. Crystal structure (4) has the poor quality that

106 indicates possible twinning and which makes R value high. Also it contains some disorder
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107 that has been squeezed [22] and the disorder in O3A and N9A atoms has been removed from
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108 the figure. Figure (1 & 2) was drawn by using ORTEP 3 program and Figure (3-5) was drawn

109 with MERCURY 3.6 program [23].

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110 2. 3. Computational methodology

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111 The electronic structure calculations of complexes (2, 4 & 5) were carried out using
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112 Gaussian09 suite of program [24]. The molecular geometries of rhenium complexes were fully

113 optimized in the gas phase employing DFT based B3LYP method [25] along with the 6-31G**

114 basis set for lighter atoms (H, C, N, O) and LANL2DZ for heavier atoms (Re and Br).

115 Harmonic frequency calculations were carried out at the same level to characterize the

116 stationary points and to ensure that the geometries are minima on the potential energy surface

117 (PES). The TD-DFT method [26] (along with 631G** basic set) was used to calculate the
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118 electronic absorption spectra of the complexes. In order to incorporate the effect of the solvent

119 around the molecule, the Polarizable Continuum Model (PCM) [27] was employed in TD-DFT

120 calculations. Natural Bond Orbital (NBO) analysis [28] was used to obtain the charges on the

121 individual atoms present in the complexes (2, 4 & 5) and the orbital occupations present in the

122 complexes.

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123 2. 4. General procedure

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124 2. 4. 1. Preparation of ligands

125 The following 2,2-dipyridylamine ligands; 1,2-bis(di-2-pyridylaminomethyl)benzene

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126 (L1), 1,3-bis(di-2-pyridylaminomethyl)benzene (L2), 1,4-bis(di-2-pyridylaminomethyl)-

127 benzene (L3), 1,3,5-tris(di-2-pyridylaminomethyl)benzene (L4) [29] and 1,2,4,5-tetrakis(di-2-

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128 pyridylaminomethyl)benzene (L5) [30] were prepared from the literature procedure.
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129 2. 4. 2. Preparation of complexes (15)
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130 A mixture of [Re(CO)5Br] (50 mg, 0.123 mmol) and the corresponding 2,2-

131 dipyridylamine ligands (L1L5) (0.123 mmol) (Scheme 1) were taken in 1:1 molar ratio in a
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132 two neck Schlenk flask fitted with a reflux condenser. The whole system was evacuated to 2-3
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133 times, nitrogen was purged and 20 ml of freshly distilled toluene was added by using syringe in

134 the nitrogen atmosphere. The respective reaction mixture was stirred and heated up to 60-70 C
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135 for 5-12 hrs and then allowed to cool to room temperature. Solvent was removed by rotatory

136 evaporator and the solid mixture was washed with hexane to remove the unreacted starting
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137 precursor and the crude product was further purified by column chromatography in neutral
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138 alumina by using hexane/ethyl acetate mixture in 1:2 ratio as an eluent to gave pale yellow or

139 yellow products.

140 [Re(CO)3(1,2-bis-DPA)Br] (1)

141 Yield: 38 mg (76 %); IR (KBr): 2020 (vs), 1909 (vs), 1892 (vs), 1601 (w), 1583 (w), 1468

142 (m), 1437 (w), 1425 (w), 1239 (w), 771 (w), 756 (w) cm1; 1H NMR (400 MHz, CDCl3, 25
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143 C): 8.98 (d, 2H, J = 1.2 Hz, CH(py)), 8.91 (t, 4H, CH(py)), 8.30 (d, 2H, J = 4 Hz, CH(py)), 7.72

144 (t, 4H, CH(py)), 7.19 (s, 4H, CH(benzyl)), 7.13 (d, 4H, J = 6.4 Hz, CH(py)), 5.24 (s, 4H, CH2) ppm;

145 ESIMS (m/z): 796.68 [M+]; UVVis {Acetonitrile, max, nm (/104 M1 cm1)}: 261 (0.95),

146 298 (1.02); Anal. Calc. for C31H24N6O3BrRe (794.67): C, 46.85; H, 3.04; N, 10.58. Found: C,

147 46.92; H, 3.33; N, 10.69 %.

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148 [Re(CO)3(1,3-bis-DPA)Br] (2)

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149 Yield: 32 mg (64 %); IR (KBr): 2020 (vs), 1908 (vs), 1884 (vs), 1601 (w), 1583 (w), 1468

150 (m), 1438 (w), 1376 (w), 1111 (w), 774 (w), 754 (w) cm1; 1H NMR (400 MHz, CDCl3, 25

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151 C): 8.95 (d, 4H, J = 5.6 Hz, CH(py)), 7.79 (s, 1H, CH(benzyl)), 7.69 (t, 4H, CH(py)), 7.40 (d, 2H,

152 J = 7.6 Hz, CH(benzyl)), 7.29 (t, 1H CH(benzyl)), 7.16 (d, 4H, J = 8.0 Hz, CH(py)), 7.07 (t, 4H,

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153 CH(py)), 5.03 (s, 4H, CH2) ppm; ESIMS (m/z): 797.21 [M+]; UVVis {Acetonitrile, max, nm

154
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(/104 M1 cm1)}: 210 (2.00), 254 (1.24), 298 (1.41); Anal. Calc. for C31H24N6O3BrRe

155 (794.67): C, 46.85; H, 3.04; N, 10.58. Found: C, 46.69; H, 3.23; N, 10.83 %.

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156 [Re(CO)3(1,4-bis-DPA)Br] (3)

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157 Yield: 40 mg (80 %); IR (KBr): 2021 (vs), 1909 (vs), 1892 (vs), 1601 (w), 1583 (w), 1467
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158 (m), 1439 (w), 1424 (w), 1111 (w), 774 (w), 756 (w) cm1; 1H NMR (400 MHz, CDCl3, 25

159 C): 8.92 (d, 2H, J = 4.4 Hz, CH(py)), 8.25 (d, 2H, J = 3.6 Hz, CH(py)), 8.21 (d, 4H, J = 4.0 Hz,
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160 CH(py)), 7.14 (d, 4H, J = 5.6 Hz, CH(benzyl)), 7.44 (t, 4H, CH(py)), 6.76 (t, 4H, CH(py)), 5.35 (s,

161 4H, CH2) ppm; ESIMS (m/z): 796.43 [M+]; UVVis {Acetonitrile, max, nm (/104 M1
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162 cm1)}: 226 (0.49), 252 (0.33), 297 (0.34); Anal. Calc. for C31H24N6O3BrRe (794.67): C,
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163 46.85; H, 3.04; N, 10.58. Found: C, 47.02; H, 3.37; N, 10.79 %.

164 [Re(CO)3(1,3,5-tris-DPA)Br] (4)

165 Yield: 41 mg (82 %); IR (KBr): 2018 (vs), 1909 (vs), 1889 (vs), 1597 (w), 1583 (w), 1467

166 (m), 1424 (m), 1375 (w), 1230 (w), 712 (w), 754 (w) cm1; 1H NMR (400 MHz, CDCl3, 25

167 C): 8.87 (d, 2H, J = 4.0 Hz, CH(py)), 8.13 (t, 6H, CH(py)), 7.07 (s, 3H, CH(benzyl)), 6.90 (d, 4H,
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168 J = 8.0 Hz, CH(py)), 6.85 (d, 6H, J = 8.0 Hz, CH(py)), 6.73 (t, 6H, CH(py)), 5.34 (s, 6H, CH2)

169 ppm; ESIMS (m/z): 978.05 [M+]; UVVis {Acetonitrile, max, nm (/104 M1 cm1)}: 227

170 (0.57), 275 (0.39), 299 (0.46); Anal. Calc. for C42H33N9O3BrRe (977.88): C, 51.59; H, 3.40; N,

171 12.89. Found: C, 51.81; H, 3.57; N, 13.03 %.

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172 [Re(CO)3(1,2,4,5-tetrakis-DPA)Br] (5)

173 Yield: 35 mg (70 %); IR (KBr): 3423 (w), 2019 (s), 1907 (s), 1892 (s), 1599 (w), 1584 (w),

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174 1468 (m), 1425 (m), 1377 (w), 1237 (w), 1152 (w), 772 (w) cm1; 1H NMR (400 MHz, CDCl3,

175 25 C): 8.31 (d, 2H, J = 3.6 Hz, CH(py)), 8.20 (d, 6H, J = 7.2 Hz, CH(py)), 7.51-7.49 (m, 8H,

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176 CH(py)), 7.29 (s, 2H, CH(benzyl)), 6.89-6.71 (m, 16H, CH(py)), 5.50 (s, 8H, CH2) ppm; ESIMS

177 (m/z): 1183.88 [M+Na]+; UVVis {Acetonitrile, max, nm (/104 M1 cm1)}: 228 (0.98), 298

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178 (0.85), 387 (0.06); Anal. Calc. for C53H42N12O3BrRe (1161.09): C, 54.82; H, 3.65; N, 14.48.

179 Found: C, 55.07; H, 3.59; N, 14.83 %.

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180 3. Results and discussion

181 3. 1. Synthesis of complexes

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182 Tricarbonylrhenium(I) complexes [Re(NN)(CO)3Br] (15) was prepared by the

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183 reaction of starting precursor with the appropriate 2,2-dipyridylamine ligands in toluene

184 medium under nitrogen atmosphere. The synthetic routes for the preparation of
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185 tricarbonylrhenium(I) complexes (15) are shown in Scheme 1. In all the complexes each DPA

186 units acting as a bidentate ligands to form a six-membered chelating ring along with rhenium
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187 metal centre which coordinates through both the pyridyl nitrogen atoms of DPA units. 2,2-
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188 dipyridylamine ligands containing aryl nitrogen atoms are the coordination sites for the

189 formation of metal complexes. Moreover, the aliphatic amine nitrogen of the DPA fragments

190 remains uncoordinated after complex formation. These synthesised tricarbonylrhenium(I)

191 complexes were isolated as neutral complexes and were soluble in dichloromethane,

192 acetonitrile and acetone, insoluble in hexane, diethyl ether and toluene. Moreover these

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193 complexes were stable in air as well as in solid state as compared to solution state and non-

194 hygroscopic in nature.

195 3. 2. Spectroscopic characterization of complexes (15)

196 The infrared spectra of all the complexes were recorded in solid KBr pellets and

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197 displays three prominent sharp bands in the (CO) carbonyl stretching frequency region for

198 the three carbonyl groups which are similar with the previously reported tricarbonylrhenium(I)

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199 complexes; fac-[Re(CO)3(NN)Br] where, NN = bpy and phen, and other fac-

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200 tricarbonylhalogenorhenium(I) complexes containing diimine ligands [31]. A sharp intense

201 higher energy band at around 2021 to 2018 cm1 and two lower energy bands with closely

spaced at around 1909 to 1907 and 1892 to 1884 cm1 has been observed. The rhenium metal

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202

203 centre in all these complexes adopts distorted octahedral geometry with three carbonyl groups

204
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arranged in a facial geometry orientation. These three carbonyl groups present in the
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205 complexes are arranged in a fac-fashion as similar with the reported rhenium complexes

206 containing carbonyl stretching frequency patterns [32]. These carbonyl stretching frequency
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207 patterns were absent in the metal free ligands. In general, the stretching frequencies of the
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208 ligands in higher frequency region are not metal-sensitive, so here we are focussing only on the

209 metal carbonyl stretching frequency region. The stretching frequencies of (C=N) and (C=C)
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210 bands for the pyridyl moieties are observed at higher wave number at around 1601 to 1583

211 cm1 region as compared to the free DPA ligands [33].

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212 The detailed proton NMR spectral data of the complexes are presented in the
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213 experimental section. The aromatic proton signals of the complexes are shifted towards

214 downfield as compared to metal free ligand signals which suggested that the DPA group of the

215 ligands are coordinating to the rhenium metal after complex formation [34]. In addition, the

216 benzyl group containing CH2 proton which shows a singlet at around 5.50-5.03 ppm which is

217 shifted to downfield as compared to free ligands. The mass spectra (m/z) of the complexes

218 were recorded in CH3CN. The parent peaks are listed in the experimental section, which are in
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219 good agreement with the expected range. ESI mass spectra of the complexes displays

220 prominent peaks corresponding to the molecular ion fragment [M+].

221 The UV-Vis spectra for the complexes were recorded in acetonitrile solution at room

222 temperature as shown in Figure 6. The electronic absorption spectra of the complexes display

223 relatively medium and/or low intensity bands in the UV-Vis region. In the electronic spectra,

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224 higher energy absorption bands (lower wavelength with high intensity) were obtained due to

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225 ligand based -* and n-* transitions and lower energy absorption bands (higher wavelength

226 with low intensity) in the visible region due to d(Re)*(L) transitions [35]. The absorption

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227 bands in the higher energy at around 210 to 228 nm and 252 to 275 nm which can be assigned

228 to ligand-to-ligand charge transfer (LLCT) and intraligand (IL) charge transfer [36]. The

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229 absorption bands in the lower energy at around 297 to 387 nm have been assigned to the

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transition of spin allowed metal-to-ligand charge transfer (MLCT) [37]. In general, these

231 complexes follows the normal trends in the electronic spectra of nitrogen containing metal
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232 complexes, which display a ligand based -* and n-* transitions in the UV region and

233 MLCT transition in the visible region.

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234 The emission spectra for these complexes were recorded in acetonitrile solution with
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235 different excitations at ex = 261, 297 and 387 nm and the spectra has shown in Figure 7. The

236 complex (1) shows two different low intense emission bands at em = 366 and 368 nm along
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237 with shoulder peaks nearer at 522 and 594 nm with two different excitations at ex = 261 and

238 298 nm. Similarly, complexes (2, 3 & 4) also shows low intense emission bands at em = 403,
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239 366 and 431 with excitations of at ex = 298, 297 & 299 nm. Moreover, the complex (5) shows
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240 high emission maxima at em = 451 nm with excitation of at ex = 387 nm [38]. Finally, it can

241 be concluded that complex (5) shows highly emission than the other complexes.

242 3. 3. Molecular structural studies

243 Single crystals were attached to a glass fibre and mounted in an Oxford Diffraction

244 Xcalibur Eos Gemini diffractometer. The crystal structure of complexes (2 & 4) with the atom
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245 numbering scheme is shown in Figure 1 & 2. The single crystal X-ray analysis reveals that

246 crystal structure (2) crystallized in monoclinic system with space group P21/n and crystal

247 structure (4) crystallized in triclinic system with space group P1 . The coordination geometries

248 of rhenium complexes on rhenium metal centre is a six-coordinated distorted octahedral

249 geometry along with three carbonyl groups (facial arrangement), one bidentate ligand and one

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250 Br-atom [39]. As expected, the X-ray crystal structure of complexes (2 & 4) confirms that two

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251 pyridyl groups of the 2,2-dipyridylamine ligands bind in a bidentate fashion in their pyridyl N-

252 atoms to the rhenium(I) metal centre in a octahedral manner. The ReN, ReBr and ReC

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253 bond lengths for the crystal structures were found to be expected range as shown in Table 2

254 [40]. The bond lengths of ReCO for both the complexes do not show any significant

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255 differences [1.925(6), 1.902(6), 1.883(6) for complex (2) and 1.902(11), 1.856(10),

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1.878(13) for complex (4)] but are consistent with those observed for similar type of diimine

257 complexes [41]. The Re(1)Br(1) bond lengths for complexes (2 & 4) are 2.6177(6) and
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258 2.6197(10) . In the complex (2) the metal-nitrogen bond lengths Re(1)N(2) and Re(1)N(3)

259 [2.203(4) & 2.203(4) ] are exactly same as compared to the complex (4) Re(1)N(2) and
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260 Re(1)N(3) [2.165(7) & 2.172(6) ]. From the crystal structure, in both complexes the two
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261 coordinated pyridyl rings of each DPA moieties are not co-planar. But compared to

262 uncoordinated pyridyl rings of DPA moieties, the coordinated pyridyl rings are planar along
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263 with Re metal centre. Here rhenium atoms are generally form two-coordinates, forming [2+4]

264 metallacycle with each rhenium bound to a pyridyl nitrogen donor from different ligands.
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265 The crystal structure of complexes has supramolecular non-covalent weak interactions
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266 in a supramolecular assembly. The crystal structure (2) shows intermolecular CH [3.433

267 ] interaction between uncoordinated pyridyl group containing H-atom and the -electron

268 cloud of the central benzene core, three different hydrogen bonding CHBr [3.027, 2.921 &

269 2.993 ] interactions has been observed; one is Br-atom (attached with Re metal) with H-atom

270 of the coordinated pyridyl moiety and other two with H-atoms of the two different CH2 groups

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271 (Figure 3). Crystal structure (4) shows two different types of CH (2.927 & 2.644 )

272 interactions [42]; one is H-atom of CH2 group with uncoordinated pyridyl moiety and another

273 one is uncoordinated pyridyl group containing H-atom with another uncoordinated pyridyl

274 moiety (Figure 4). Also crystal structure (4) shows lone pair interaction, such as CO

275 (2.672 ) interaction between O-atom (attached ReCO) containing lone pair and -electron

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276 cloud of the central benzene moiety (Figure 5) [43].

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277 3. 4. Optimized structural geometry

278 The geometries of all the complexes are found to be closed shell structures and no

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279 parameters has been constrained during their optimization. The geometric parameter such as

280 bond lengths and bond angles of complexes are listed in Table S1-S3. Our calculated bond

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281 lengths and bond angles for complexes (2 & 4) are very close to the experimental values except

282
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for a slight discrepancy in N(2)-Re(1)-C(2), N(3)-Re(1)-C(3) and C(2)-Re(1)-C(3) bond angles

283 in both the complexes. Moreover, the geometric parameters for complex (5) are in well
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284 agreement with the values obtained for complexes (2 & 4) as it lies within the same range of
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285 values obtained for the other two complexes. This agreement of our calculated data with the
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286 single crystal X-ray structural data gives a positive indication on the reliability of the DFT

287 based B3LYP method.

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288 3. 5. Charge distribution

289 The atomic charges of the complexes (2, 4 & 5) were calculated by NBO analysis and
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290 are listed in Table S4. The atomic charges on the Re atom for the three complexes are in the
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291 ranges between 0.9884 and 0.9615 (e) which are lower than the formal charge of +1. As

292 expected the charges on the carbon atoms of the carbonyl groups are all positive, whereas the

293 oxygen atoms are characterized with a negative charge. The negative charge on the Br atom is

294 maximum for complex (4) and least for complex (5), whereas the negative charges on the N3

295 atom are slightly higher than N1 and N2 in all three complexes. It should be noted that the

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296 highest negative charge on the Br atom in complex (4) is a reflection of the lowest negative

297 charge on the Re atom. The population of 5d orbitals (5dxy, 5dxz, 5dyz, 5dx2y2 and 5dz2) of the

298 metal atom for the three rhenium complexes are shown in Table S5. In free Re (+1) state, the

299 population of 5dxy, 5dxz and 5dyz orbitals are 2.0, 2.0 and 2.0 (e) and the other two (5dx2y2 and

300 5dz2) orbitals remain vacant. On complex formation, the 5d orbital (5dxy, 5dxz, 5dyz, 5dx2y2 and

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301 5dz2) attains population of 1.5154, 1.2982, 1.5188, 1.1323 and 1.2243 (e) for complex (2),

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302 1.3431, 1.1712, 1.2330, 1.3726 and 1.5636 (e) for complex (4) and 1.3041, 1.1502, 1.2918,

303 1.3982 and 1.5373 (e) for complex (5) respectively. In comparison to free Re (+1) state, some

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304 decrease in populations for the 5dxy, 5dxz and 5dyz orbital and an increase in the populations of

305 5dx2y2 and 5dz2 orbital can be observed in all these complexes. It is also observed that orbital

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306 population for complexes (4 and 5) are somewhat equal but the same trend is not followed in

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the complex (2). Though all the ligands (L2, L4 and L5) coordinated to the rhenium metal

308 through the same nitrogen N1 and N3 atoms but the ligands are different in nature (number of
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309 pyridyl rings) which can be the reason for the differences in 5d orbital populations in complex

310 (2) as compared to complexes (4 & 5).

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311 3. 6. Frontier molecular orbital and absorption spectra

312 The molecular orbital representation of the complexes along with their HOMO,
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313 LUMO energies and HOMO-LUMO energy gaps are shown in Figure 8. The HOMO-LUMO

314 energy gap is an important tool which determines the kinetic stability and chemical reactivity
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315 of a molecule. The lower HOMO-LUMO energy gap is a suitable condition where a molecule
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316 can be excited easily whereas a higher energy gap results in a higher kinetic stability but lower

317 chemical reactivity of the molecule. The HOMO-LUMO energy gap is maximum 3.845 (eV)

318 for complex (5), least 3.533 (eV) for complex (4) and 3.749 (eV) for complex (2). From the %

319 contribution of molecular orbital analysis as shown in Table S6, it is can be seen that the

320 HOMO (about 63%) is located on the Br atom for complex (2), whereas for complexes (4 & 5)

321 it is located (more than 80%) on the ligand itself. In HOMO1 orbital, the major % of
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322 molecular orbital for complex (5) is located on the Re metal whereas, for complex (4) it is

323 located on the ligand itself.

324 Theoretically, the electronic absorption spectra were calculated using the TD-DFT

325 method in acetonitrile solvent employing PCM method. The calculated and the experimental

326 absorption spectral values, energy gap, the electronic transitions and dominant excitation

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327 character for various singlet states of complexes are listed in Table 3. The HL transition for

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328 complex (2) corresponds to LLCT character i.e, (Br)*(L) transfer whereas, for complex (4

329 & 5) it corresponds to ILCT character [44]. The MLCT transitions i.e, d(Re)*(L) for

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330 complex (2) were observed at around 297, 257 and 254 nm, for complex (4) at around 298 and

331 292 nm whereas, for complex (5) it is observed at 298 nm. These results are in good agreement

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332 with the experimental results except few higher energy absorptions (at around 257 and 254 nm)

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which belongs to MLCT transitions resulting from the d(Re)*(L) transitions. The ILCT

334 and LLCT transitions were observed in both high and low energy regions as indicated in Table
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335 3.
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336 4. Conclusion
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337 In summary, we have synthesised new series of tricarbonylrhenium(I) complexes

338 containing 2,2-dipyridylamine derivative ligands which shows supramolecular non-covalent

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339 interactions with supramolecular assembly. Moreover, single crystal X-ray diffraction and

340 infrared spectra details reveals that the carbonyl groups in the tricarbonylrhenium(I) complexes
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341 are in facial arrangement. The molecular structure of complexes [Re(NN)(CO)3Br] are found
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342 to possess distorted octahedral geometry around the rhenium metal centre along with three

343 carbonyl groups in a facial arrangement, a bidentate ligand and one Br-atom. The molecular

344 orbital diagram and electronic transitions of complexes fac-[Re(NN)(CO)3Br] have been

345 calculated with the time-dependent DFT method which are in good agreement with the

346 experimental values.

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347 Acknowledgements

348 S. Sangilipandi thanks to UGC-BSR-RFSMS New Delhi, India for providing financial

349 support in the form of Meritorious Fellowship. A.K.C thanks Computer Centre, NEHU

350 Shillong for providing computing facilities. We thank DST-PURSE SCXRD, NEHU-SAIF

351 Shillong for providing Single crystal X-ray analysis and other spectral studies.

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352 Appendix A. Supplementary materials

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353 CCDC 1432548 (2), 1432549 (4) contains the supplementary crystallographic data for

354 this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif,

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355 by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic

356 Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033.

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357 References AN
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432 2523.

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455 Saffon, R. Kruszynski, Z. Mazurak, J. Organomet. Chem., 696 (2011) 3068.

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456 (b) B. Machura, R. Penczek, R. Kruszynski, Polyhedron, 26 (2007) 2470.

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457
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458 Chart 1. Ligands used in this study.

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459

460 Scheme 1. Preparation of metal complexes (15).

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461

462 Fig. 1. Molecular structure of complex [Re(CO)3(1,3-bis-DPA)Br] (2) with 50% probability

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463 thermal ellipsoids. Solvent molecule and hydrogen atoms are omitted for clarity.

464

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465

466 Fig. 2. Molecular structure of complex [Re(CO)3(1,3,5-tris-DPA)Br] (4) with 50% probability
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467 thermal ellipsoids. Hydrogen atoms are omitted for clarity.

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468

469 Fig. 3. View of crystal structure (2) shows intermolecular CH interaction (green) on H(8)

470
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atom (H-atom of the coordinated pyridyl moiety) with -electron cloud of the central benzene

471 moiety and three different CHBr hydrogen bonding interactions (magenta, orange and
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472 blue). Symmetry codes: CH(21A)Br(1) = (1+x, y, z); CH(10)Br(1) &
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473 CH(14B)Br(1) = (1/2+x, 1.5y, 1/2+z).

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474
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475 Fig. 4. View of crystal structure (4) shows two different types of intermolecular CH

476 interactions (green); One is uncoordinated pyridyl group containing H(36)-atom with the
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477 uncoordinated pyridyl moiety and the another one is benzyl group CH2 containing H(10)-atom

478 with another uncoordinated pyridyl moiety.

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479

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480 Fig. 5. View of crystal structure (4) shows lone pair [CO] (green) interaction between

481 O(3)-atom of CO group and -electron cloud of the central benzene moiety.

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482

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483

484 Fig. 6. Absorption spectra of complexes (15).

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485

486 AN
Fig. 7. Emission spectra of complexes (15).
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487

488 Fig. 8. HOMO, LUMO energies and HOMO-LUMO energy gap of complexes (2, 4 & 5).

489

490

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491 Table 1 Crystallographic data and structure refinement details of complexes (2 & 4).

Complexes [2] [4]

Empirical formula C62H50Br2N12O7Re2 C42H33BrN9O3Re

Formula weight 1607.36 977.88
Temperature (K) 290(2) 294(2)

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Wavelength () 0.71073 0.71073
Crystal system Monoclinic Triclinic
Space group P21/n P-1

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a ()/ () 12.6128(3)/90 8.9343(4)/92.656(5)
b ()/ () 16.5797(5)/97.651(3) 15.2005(8)/97.738(5)
c ()/ () 14.2257(4)/90 17.2311(12)/101.720(4)

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Volume (3) 2948.34(14) 2263.9(2)
Z 2 2
Density (calc)/Mg/m3 1.811 1.435
Absorption coefficient ()/mm1 5.522 3.611

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F(000) 1564 964
Crystal size (mm3) 0.21 0.18 0.17 0.42 0.05 0.04
range ()
Index ranges
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3.14 to 28.75
-15 h 14, -21 k 16, -16
3.02 to 28.70
-11 h 11, -19 k 18, -23
l 19 l 22
Reflections collected 14091 19112
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Independent reflections 6755 [R(int) = 0.0368] 10189 [R(int) = 0.0708]
Completeness to = 25.00 99.7 % 98.9 %
Absorption correction Semi-empirical from Semi-empirical from
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equivalents equivalents
Max. and min. transmission 0.4537 and 0.3901 0.8690 and 0.3123
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Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2

Data/restraints/parameters 6755/115/427 10189/108/559
Goodness-of-fit on F2 1.033 1.009
Final R indices [I>2(I)]* R1 = 0.0417, wR2 = 0.0766 R1 = 0.0763, wR2 = 0.1533
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R indices (all data) R1 = 0.0674, wR2 = 0.0870 R1 = 0.1230, wR2 = 0.1790

Largest diff. peak and hole (e.3) 1.526 and 0.875 2.752 and 1.878
CCDC no. 1432548 1432549
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492 *Structures were refined on F02: wR2 = [[w(F02Fc2)2]/w(F02)2]1/2, where w1 =

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493 [(F02)+(aP)2+bP] and P = [max(F02, 0)+2Fc2]/3.

494

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495 Table 2 Selected bond lengths () and bond angles () of complexes (2 & 4).

[2] [4]

Re(1)N(2) 2.203(4) 2.165(7)

Re(1)N(3) 2.203(4) 2.172(6)
Re(1)Br(1) 2.6177(6) 2.6197(10)

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Re(1)C(1) 1.925(6) 1.902(11)
Re(1)C(2) 1.902(6) 1.856(10)
Re(1)C(3) 1.883(6) 1.878(13)
N(2)Re(1)N(3) 80.37(14) 81.1(2)

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Br(1)Re(1)N(2) 85.09(11) 84.28(16)
Br(1)Re(1)N(3) 85.30(11) 84.93(16)
Br(1)Re(1)C(1) 88.47(17) 93.8(3)

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Br(1)Re(1)C(2) 95.50(18) 91.5(13)
Br(1)Re(1)C(3) 177.82(17) 179.1(3)
496

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497 Table 3 The energy gap, theoretical and experimental absorption bands, the electronic

498 transitions and dominant excitation character for various singlet states of complexes.

Most important Calculated Energy gap Oscillator Dominant excitation Experimental

orbital excitations (nm) E (eV) strength (f) character (nm)
Complex (2)

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HL 349.12 3.749 0.0003 BrL2 (LLCT)
HL+2 305.81 4.271 0.1854 BrL2 (LLCT)
H-3L+1 297.21 4.559 0.0080 ReL2 (MLCT) 298
HL+4 289.36 4.525 0.1014 BrL2 (LLCT)

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H-9L 259.87 5.255 0.0149 BrL2 (LLCT)
H-3L+3 257.28 5.102 0.0033 ReL2 (MLCT)
H-2L+7 255.99 5.506 0.0153 L2L2 (IL)

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H-3L+5 253.55 5.198 0.0886 ReL2 (MLCT) 254
H-6L+1 252.28 5.215 0.0281 L2L2 (IL)
Complex (4)

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HL 347.89 3.533 0.0012 L4L4 (IL)
HL+6
H-2L+4
H-4L
302.56
300.78
298.58
4.772
4.886
4.536
AN 0.0532
0.0071
0.0649
L4CO (LLCT)
BrL4 (LLCT)
ReL4 (MLCT) 299
H-4L+1 298.57 4.536 0.0861 ReL4 (MLCT)
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HL+2 297.80 4.161 0.1100 L4L4 (IL)
H-2L+2 295.98 4.407 0.0691 BrL4 (LLCT)
H-4L+1 292.43 4.548 0.0411 ReL4 (MLCT)
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H-5L 276.96 4.735 0.0197 L4L4 (IL)

H-1L+4 275.38 4.830 0.0061 L4L4 (IL) 275
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H-1L+7 274.46 5.004 0.0208 L4L4 (IL)

Complex (5)

HL 344.31 3.845 0.0001 L5L5 (IL) 387

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HL+2 304.77 4.393 0.0405 L5L5 (IL)

H-5L+1 302.99 4.654 0.0880 L5L5 (IL)
H-1L+2 298.21 4.413 0.0324 ReL5 (MLCT) 298
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H-3L+7 295.79 4.905 0.0010 L5L5 (IL)

H-7L 295.39 4.863 0.0017 BrL5 (LLCT)
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HL+6 293.83 4.673 0.0517 L5L5 (IL)

499 MLCT = Metal to ligand charge transfer, LLCT = Ligand to ligand charge transfer and IL =

500 Intraligand charge transfer.

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Highlights

2,2-dipyridylamine based tricarbonylrhenium(I) complexes.

Complexes have supramolecular non-covalent CH, anion (CO)

interactions.

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TDDFT calculations shows the values are good agreement with the

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