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Abstract
Crystalline hybrids incorporating ionic and coordinate bonding properties have been reported to exhibit
high thermal stability as well as strong optical properties. Four new CuX (X = Cl, Br, I) hybrids were
synthesized in various reaction conditions using a cationic ligand containing multiple coordination sites,
prompting the formation of robust, highly luminescent materials. Three of these compounds exhibit bright
emission in the 550-600nm range under 365nm excitation. Two of these luminescent compounds are
crystalline, varying only in the cuprous halide chain. Structural differences seem to differ solely as a
result of halide variation, demonstrating potential for emission and bandgap tunability. High thermal
stability and apparent quantum yields make them valuable candidates for further exploration and possible
The introduction of solid-state lighting (SSL) has brought newer and more efficient
technologies to consumers.1 Light emitting diodes (LEDs), the most common form of SSL, have
become popular due to their longer lifetimes and reduced energy consumption in comparison to
incandescent or fluorescent lightbulbs; 12W LED bulbs have a lifetime of around 25,000 hours,
while 15W compact fluorescent bulbs (CFLs) and 43W incandescent bulbs have lifetimes of
10,000 and 3,000 hours, respectively.2 The U.S. Department of Energys Energy Star campaign
includes a transition to SSL and connected lighting as part of its energy conservation efforts,
predicting $630 billion in energy cost savings if their SSL goals are achieved.3 As of the writing
of this report, the SSL transition is in full effect across the U.S., with white LEDs (WLEDs) of
LEDs often require the use of rare-earth elements (REEs). Commercial phosphor-converted
white LEDs (PC-WLEDs) such as those used on smartphones and bike lights (Figure 1) are
composed of a blue InGaN emitting diode coated with YAG:Ce3+, a yellow-emitting phosphor.6,7
Derivatives of YAG:Ce3+ are particularly desirable due to internal quantum yields (IQY)
exceeding 85%.6 High demand of REEs may lead to future shortages, making REE-free
phosphors highly desirable alternatives for efficient lighting.7 Of the alternatives currently being
studied, the candidates which display arguably the highest potential for future commercial use
1990s in the form of periodically organized mesoporous materials.8,9 Eventually, research began
interesting materials that combine the properties of each into a single crystal lattice, resulting in
new properties not present in either individual material.10-12 Early research revolved around
metal organic frameworks (MOFs), materials which have developed high potential for sensing,
gas separation, photovoltaics, etc.13-15 With the onset of SSL, researchers began exploring the
potential of hybrid phosphors, the first being luminescent MOFs containing metal centers with
hybrid crystals featuring metal clusters. Such hybrids have been found to have tunable emission
functional groups on organic ligands.18-22 Notably, Cu halide-based hybrids (especially CuI) have
been studied extensively due to their tendency to form clusters with potential for favorable
optical properties.23-26 The basis for these luminescent hybrids involve coordination between a
N, S, or P site on an organic ligand.27,29, 33-35 Most of these phosphors, however, are limited in
their potential for commercial use due to issues such as poor robustness and being exclusively
UV-excitable.28 Attempts to increase stability have resulted in ionic compounds similar to lead
halide perovskites which, while containing inorganic and organic components, lack actual
coordinate bonds between components. Such a deficiency removes potential for metal-ligand or
A recent publication reported the synthesis of structures which combine the properties of
coordinate and ionic hybrids (Figure 2).36 Cationic functional groups on organic ligands with
multiple coordination sites prompted the formation of anionic CumXn clusters such as 1D-Cu2I42-
and 2D-Cu4I62- (Figure 3) without interacting with the cluster itself. Instead, a different N or P
atom would coordinate with the metal cluster, yielding phosphors with combined properties of
coordinate and ionic bonding, including high thermal stability and optical efficiency. In this
project, three new crystals are presented, each based on a cuprous halide cluster containing a
benzotriazole (bzt) ligand, two of which are luminescent. Alkylation of the bzt NH site allows for
the addition of a cationic amminium group, while binding with the metal ion is directed toward
one or both of the other N atoms in the triazole ring. By further adjusting the halide in the metal
cluster, there appears to be potential for optical tunability. The ionic properties of these structures
as well as the tendency of the bzt ligands to chelate yield high chemical and thermal robustness.
While more work can be done to increase blue-light excitability, this group of phosphors shows
high potential for an entire family of phosphors which could be commercial implemented.
Experimental
Materials: All materials were purchased from commercial suppliers (Alfa Aesar, Sigma-
Aldrich) and used as reagent grade. Organic syntheses were performed using standard
equipment, while crystal syntheses were carried out in 20mL glass scintillation vials.
4): A mixtures of bzt (5.00 g), 1-bromo-3-chloropropane (3.14 mL, 1.0 eq) and NaOH (0.2 g, 5
mmol) was dissolved in methanol (50 mL) and refluxed at 120C for 5.5 hours. Solvent was
Clpr-bzt (0.025 mol) was fully dissolved in acetone (20 mL), and KI (5.000g) was added. This
mixture was stirred at room temperature for 2 hr. The solution was filtered, followed by addition
of trimethylamine (tma, 2 mL). White precipitate formed overnight. Crude product was filtered
Synthesis of 1D-CuI2(dmbtea) (1): Stock solutions of saturated KI/CuI were prepared via
sonification and filtration. Saturated stock solution (2 mL) was pipetted into a 20 mL glass
scintillation vial. Acetonitrile (2 mL) was then added slowly, followed by addition of dmbtea (1
mmol) in methanol (2 mL); this reaction is known as a three-layer synthesis. The reaction
proceeded open-air at room temperature. Yellow plate-shaped crystals formed overnight and was
extracted via filtration. The sample was left to dry for two days after washing with methanol and
distilled water. This three layer synthesis was utilized in a previous paper36 with exception of a
saturated first layer; this modification was implemented to further encourage cluster formation,
Synthesis of 1D-CuBr2(dmbtea) (2): Stock solutions of saturated KBr/CuBr were prepared via
sonification and filtration. Saturated stock solution (2 mL), acetonitrile (2 mL), and dmbtea (1
mmol) in methanol (2 mL) were pipetted into a 20 mL glass scintillation vial, identical to the
synthesis of 1. The reaction proceeded open-air at room temperature. Yellow rod-shaped crystals
formed overnight and were extracted via filtration. The sample was left to dry for two days after
that of compound 2, however, ethanol was used instead of methanol to dissolve dmbtea. A green
powder formed overnight and was collected via filtration. Single crystal x-ray diffraction could
Synthesis of CuxCly(dmbtea)z (4): Stock solutions of saturated NaCl/CuCl were prepared via
sonification and filtration. Saturated stock solution (4 mL), acetonitrile (2 mL), and dmbtea (1
mmol) in 2 mL methanol were pipetted into a stainless steel autoclave for hydrothermal
synthesis. The vessel was kept at 180C under autogenous pressure for 24 hours, forming
transparent, rod-shaped crystals. The sample was left to dry for two days after washing with
methanol and distilled water. Single crystal x-ray diffraction could not be performed due to time
were performed on compounds 1 and 2 by a collaborator due to lack of equipment at the research
collaborators facility were used to collect single crystal data using synchrotron radiation. The
structures were solved by direct methods and refined by full-matrix least-squares on F2 using the
Powder X-Ray Diffraction (PXRD): PXRD patterns were collected by Competition Entrant on
40 was used with a scan speed of 2 min-1 at an operating power of 40 kV and 44 mA.
at room temperature. Powder coatings on non-emissive glass slides were measured using a
preliminary test excitation of 365nm. Peak emissions found at 365nm excitation were then measured
Shimadzu UV-3600 spectrophotometer. Data was collected with a wavelength range of 350-700
nm. Crystalline samples were ground into powder and distributed evenly between calibrated
quartz slides for measurement. The optical bandgap of both compounds was estimated by
analyzer. Samples were loaded onto a platinum pan and heated with a ramp rate of 10 C min-1
DEMASLEDs with Scotch double-sided tape, then coated with commercial and synthesized
Ligand Synthesis: This report extends the design from a previously mentioned publication by
using longer alkyl halides to create similar bzt ligands.36 Ligands with alkyl chains of varying
length were also studied; the use of dmbtea in three-layer crystallization was unique in its
relatively high yield and reactive spontaneity with both CuI and CuBr at room temperature.
Crystallization conditions for other ligands with varying alkyl chain lengths have yet to be found.
The synthesis of dmbtea is shown in Figure 4. The H1NMR spectrum of clpr-bzt (Figure 5) was
taken before vacuum dry, resulting in the presence of methanol peaks. KI was used to prepare the
ligand as a salt to be dissolved in methanol instead of an ion in solution for facile storage and
synthesis.
Structure Analysis: The previously reported phosphor36 using a bzt-based ligand, 1D-
Cu4I6(tpp)2 (bttmm)2 (Figure 6b), was synthesized via a 0D precursor (triphenylphosphine = tpp,
the use of a precursor, thus dmbtea is the sole ligand present in all structures. A quasi-chelating
effect is observed in compounds 1-3; two nitrogen atoms from the triazole ring of dmbtea
coordinate to neighboring Cu+ ions on a 1D-Cu2X3- chain (Figure 6a). The Cu2X3- cluster has
not been previously reported; extensive studies have yet to be performed on the effects of ligand
structure on cluster type and dimensionality. Evidently, the formation of this chain was only
possible due to the lack of the precursor; the two nitrogen bonding sites occupy what would
crystal system, while compound 2 is orthorhombic. The differences in cell volume and
measurements are believed to be solely the result of the increased size of the iodide anion, as the
compounds share the same dimensionality and bonding patterns with dmbtea. Cell angles
indicate that both structures contain considerably less stress than 1D-Cu4I6(tpp)2 (bttmm)2,
consistent with increased thermal stability (compounds 1 and 2 decompose around 250C, while
1D-Cu4I6(tpp)2 (bttmm)2 begins decomposing at 200C)36. Cu-L bond lengths differ for each
bidentate N atom, measured to be 2.109 /2.060 for compound 1 and 1.987 /2.057 for
compound 2, accounting for the differences in crystal systems and unit cell measurements
between compounds. Unit cell diagrams of compounds 1 and 2 are shown in Figure 7. Complete
The PXRD patterns for compounds 1-4 are shown in Figure 8a-d. Compounds 2 and 3
exhibit identical low-angle peaks of different intensity. While the structure of 3 has not been
determined, solvent molecules disruption during crystallization may have caused the ligand to
coordinate at different positions or angles, resulting in a different colored compound. The overall
structure of compound 3 is likely very similar to compound 2, as the two compounds have nearly
Compounds 1 and 2 were also kept at 80C under autogenous pressure for 10 days with
PXRD measurements taken before and after; low angle-peaks remained consistent for both
measurements (Figures 9a-b and 10a-b). This is promising for SSL use, as lifetimes of cheaper
phosphors are often a major concern when considering commercial use. Further tests may
include moisture and higher temperature stability; more importantly, these tests cannot lead to
luminescent quenching if the compounds are to be explored for commercial use. Visibly and
structurally, both compounds seem to exhibit stability through the 10-day thermal test, but
further tests will be held off until IQY measurements can be performed.
Compounds 1-3 also exhibit high thermal stability under extreme conditions, with
negligible decomposition until around 250C, shown in the TGA curves (Figure 11). In general,
the decomposition of hybrid phosphors equates to the evaporation of organic ligands. For hybrids
with neutral components, ligand loss occurs due to cleavage of a Cun+-L coordinate bond. In
formed by the cationic ligands and halide anions. Both the Cun+-L and Cu-X bond need to be
cleaved for this to occur. Enhanced thermal stability may be derived from extra energy necessary
As mentioned earlier, the structure of compound 4 was not determined due to time
constraints. However, we hypothesize that a coordinate bond is not present in the structure, as it
does not exhibit visible emission under UV, blue, or 254nm light. Compound 4 also exhibits
negligible decomposition through 600C, shown in the TGA curve (Figure 11), implying high
bonding energies. It is hypothesized that the crystal may be purely an ionic structure. This is not
surprising due to the bonding radius of the chloride anion (~99pm) compared to those of bromide
(~114pm) and iodide (~133pm),37 resulting in a tighter metal chain and reduced space for a
ligand to coordinate. The lack of coloration may also indicate the crystals ionic nature (although
it cannot be used as the sole identifier); crystal field theory implies the d-orbitals of the Cu ions
Optical Properties: The room temperature photoluminescent (PL) spectra of compounds 1-3 are
shown in Figure 12. Compound 1 exhibits strong yellow emission (555 nm), visibly blue-shifted
from the orange emission of compound 2 (595 nm). Peak emission differences between the two
can be used to produce white light of different temperatures (i.e. warm and cool white
light are produced using different intensities of red and blue light)38. Compound 1 exhibits
significantly brighter emission. Using the Kubelka-Munk function from diffuse reflectance
measurements, optical bandgap for compounds 1 and 2 are estimated to be ~2.35 eV and ~2.46
eV, respectively (Figure 13), which may imply cluster-centered (C-C) or halide-ligand (X-L)
centered transitions being responsible for emission, consistent with the electronegativity of each
halide (I- < Br-). Density functional theory (DFT) measurements may be conducted in future
hypothesize the type of transition (e.g. singlet-singlet, singlet-triplet) and for complete Jablonski
analysis, however, the consistency of both structures in nearly every aspect aside from formulaic
While IQY data could not be obtained due to equipment malfunctions, relative excitation
spectra were taken using the Varian Cary Eclipse spectrometer (Figure 14). Separate emission
spectra under 455nm excitation are also shown in Figure 12. Compound 1 exhibits strong 555nm
emission under 350-460nm excitation. However, compound 2 exhibits 595nm emission under
excitation less than 400nm, dropping off at lower energies. This may be a result of the higher
bandgap and structural composition of compound 2; more energy is required for excitation to
occur for a hypothesized bromide-ligand transition. LED and UV images of compounds 1, 2, and
YAG:Ce3+, the commercially favored yellow phosphor, are shown in Figures 15 and 17.
Microscope images of compounds 1-4 are shown in Figure 16. Optical properties of compounds
Four new compounds were synthesized with the intent of creating highly stable and
luminescent compounds by combining coordinate and ionic bonds. Three of these compounds,
two unique (1 and 2), exhibited strong optical properties, including strong luminescence and
bandgap tunability based on formulaic halide variation. Differences between copper iodide and
copper bromide structures appear to be purely a result of halide variation, showing promise for
bzt ligand types to be tunable using discrete variables. Further structural and thermal analyses
were performed revealing high robustness throughout, hypothesized to be a result of the quasi-
chelating ligand, a new phenomenon which was possible due to the direct crystallization of CuX
with the ligand as opposed to the use of a precursor. Optical patterns were analyzed and used to
present a strong hypothesis for the transition type without the use of DFT calculations.
Tunability based on halide variation shows promise for producing commercials white LEDs of
different temperatures. Prototype LEDs were created and photographed; the CuI based structure
exhibits high apparent IQY and seems comparable to YAG:Ce3+. This study represents a
benchmark for expansion of bzt ligand exploration with the potential to create family of
structures containing bzt-based ligands with varying alkylated chains, possibly resulting in a
my lack of experience, significant time was spent learning analyses procedures and lab safety.
Additionally, while Dr. Wei Liu, my mentor, and other lab members provided invaluable
guidance, I am still learning the basics of organic syntheses and reaction design. Mentioned first
in the experimental section, I would like to reiterate thanks to Dr. Liu for helping facilitate ligand
proposals. Aside from time constraints, lack of equipment at the research facility was another
limiting factor. SCXRD and IQY data could not be readily collected. Additionally, tasks such as
DFT and HOMO-LUMO measurements using advanced software such as Gaussian 9 are
transition responsible for emission. With time and higher education, I would gladly take the
opportunity to review this report with expanded knowledge of organic chemistry and hybrid-
specific analyses.
As mentioned earlier, compounds 2 and 3 exhibit little to no emission under 455nm light.
The orange emission of these two phosphors is desirable for white light temperature tunability,
so future work with 1D-CuBr chains may be focused on decreasing the bandgap. Determining
which transitions are responsible for emission is important in formulating a new approach,
making DFT measurements ever more valuable. Developing synthesis conditions for a
cluster formation. Dr. Liu recently came across a publication which reported CuX-tetrazolide
crystals, featuring the tetrazolide anion coordinating with cationic clusters.24 After reading the
publication, I thought it would interesting to explore potential for other reverse coordinate-
ionic hybrid structures using five-member heterocyclic rings. While pyrrole proved to be inert,
some luminescent powders were obtained using 1H-imidazole, methyl-imidazole, and 1H-
triazole via hydrothermal syntheses. Structures could not be determined for these compounds due
to lack of single crystal formation. Sulfur-containing organic compounds may have higher
potential for forming anionic ligands due to having higher pH values than nitrogen-containing
compounds. Preliminary tests have been run on a few compounds with no results.
Cluster formation patterns are also of interest. As of this report, there seems to be little
correlation between the organic ligand and the dimensionality of the anionic CuX cluster. The
Cu2X3- cluster is a new orientation. The dimensionality of clusters is important in that it denotes
Figure 4 Synthesis of dmbtea via clpr-bzt precursor. Isomers of clpr-bzt were not separated, as I was
allowed to run only basic columns as learning experience; more complex columns were deemed unsafe.40
Figure 6 Solved structure for (a) compounds 1-2, hypothesized structure for 3. (b) Previously reported
crystal containing bzt ligand and tpp.36 (c) Example bzt ligands as ionic salts. White = C, blue = N, cyan =
Cu, pink = halide, green = P. H atoms have been omitted for clarity.36,39
Fig. 8 Fig. 10
d.
c. b.
b.
a.
a.
Fig. 9
Figure 8 PXRD patterns for (a) compound
1. (b) compound 2. (c) compound 3. (d)
compound 4.40
Figure 9 PXRD patterns for (a) compound
b. 1 (b) compound 1 after 10 d. at 80C.40
Figure 10 PXRD patterns for (a)
compound 2 (b) compound 2 after 10 d. at
80C.40
a.
Fig. 11 Fig. 13
Fig. 12 Fig. 14
a. b. c. d.
Figure 15 3.0-3.2 V 455nm DEMSLED coated with (a) no compound. (b) YAG:Ce3+. (c) compound 1. (d)
compound 2.40
a. b.
Fig. 17
Table 1 Crystal data for compounds 1, 2, and previously reported luminescent hybrid with bzt-based
ligand.36,40
(C12H19N3Cu2I3)
(C12H19N3Cu2Br3)
1) Pust, Philipp; Schmidt, Peter J.; Schnick, Wolfgang (2015): A revolution in lighting. In Nat Mater 14
(5), pp. 454458. DOI: 10.1038/nmat4270.
2) United States Department of Energy (2017): How Energy-Efficient Light Bulbs Compare with
Traditional Incandescents. Available online at https://energy.gov/energysaver/how-energy-efficient-light-
bulbs-compare-traditional-incandescents.
3) Penning, Julie; Stober, Kelsey; Taylor, Victor; Yamada, Mary: Energy Savings Forecast of Solid-State
Lighting in General Illumination Applications. Prepared for the U.S. Department of Energy Solid-State
Lighting Program. United States Department of Energy. Washington, D.C. Available online at
https://energy.gov/sites/prod/files/2016/10/f33/energysavingsforecast16_0.pdf.
4) Lowe's (2017): Lowe's - Lighting and Ceiling Fan Department. Available online at
https://www.lowes.com/c/Light-bulbs-Lighting-ceiling-fans.
5) The Home Depot (2017): Home Depot - Lighting and Ceiling Fan Department. Available online at
http://www.homedepot.com/b/Lighting-Ceiling-Fans/N-5yc1vZbvn5.
6) Setlur, A. (2009): Phosphors for LED-based solid-state lighting. In The Electrochemical Society
Interface 16 (4), p. 32.
7) Massari, Stefania; Ruberti, Marcello (2013): Rare earth elements as critical raw materials. Focus on
international markets and future strategies. In Resources Policy 38 (1), pp. 3643. DOI:
10.1016/j.resourpol.2012.07.001.
8) Zhu, Yun-Pei; Yuan, Zhong-Yong (2015): Mesoporous Organic-Inorganic Non-Siliceous Hybrid
Materials. Basic Principles and Promising Multifunctionality. 1st ed.: Springer-Verlag Berlin Heidelberg
(SpringerBreifs in Molecular Science).
9) Inagaki, S.; Fukushima, Y.; Kuroda, K. (1993): Synthesis of highly ordered mesoporous materials from
a layered polysilicate. In Journal of the Chemical Society, Chemical Communications (8), pp. 680682.
DOI: 10.1039/C39930000680.
10) Inagaki, Shinji; Guan, Shiyou; Ohsuna, Tetsu; Terasaki, Osamu (2002): An ordered mesoporous
organosilica hybrid material with a crystal-like wall structure. In Nature 416 (6878), pp. 304307. DOI:
10.1038/416304a.
11) Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D. (1999): Organic-Inorganic Hybrid Materials as
Semiconducting Channels in Thin-Film Field-Effect Transistors. In Science 286 (5441), p. 945. DOI:
10.1126/science.286.5441.945.
12) Wen, Xiao-Dong; Hoffmann, Roald; Ashcroft, N. W. (2013): Two-Dimensional CdSe Nanosheets
and their Interaction with Stabilizing Ligands. In Adv. Mater. 25 (2), pp. 261266. DOI:
10.1002/adma.201203184.
13) Abdelhamid, Hani Nasser; Bermejo-Gmez, Antonio; Martn-Matute, Beln; Zou, Xiaodong (2017):
A water-stable lanthanide metal-organic framework for fluorimetric detection of ferric ions and
tryptophan. In Mikrochimica Acta 184 (9), pp. 33633371. DOI: 10.1007/s00604-017-2306-0.
14) Horcajada, Patricia; Gref, Ruxandra; Baati, Tarek; Allan, Phoebe K.; Maurin, Guillaume; Couvreur,
Patrick et al. (2012): MetalOrganic Frameworks in Biomedicine. In Chemical Reviews 112 (2),
pp. 12321268. DOI: 10.1021/cr200256v.
15) Wang, Hao; Lashkari, Elham; Lim, Hyuna; Zheng, Chong; Emge, Thomas J.; Gong, Qihan et al.
(2016): The moisture-triggered controlled release of a natural food preservative from a microporous
metal-organic framework. In Chemical Communications 52 (10), pp. 21292132. DOI:
10.1039/C5CC09634K.
16) Chen, Ling; Ye, Jia-Wen; Wang, Hai-Ping; Pan, Mei; Yin, Shao-Yun; Wei, Zhang-Wen et al. (2017):
Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence
8, 15985 EP -. DOI: 10.1038/ncomms15985.
17) Cui, Yuanjing; Yue, Yanfeng; Qian, Guodong; Chen, Banglin (2012): Luminescent Functional
MetalOrganic Frameworks. In Chemical Reviews 112 (2), pp. 11261162. DOI: 10.1021/cr200101d.
18) Deibert, Benjamin J et al. (2016): High-Performance Blue-Excitable Yellow Phosphor Obtained from
an Activated Solvochromic Bismuth-Fluorophore MetalOrganic Framework. In Cryst. Growth Des 16
(8), pp. 41784182.
19) Huang, Xiaoying; Li, Jing; Zhang, Yong; Mascarenhas, Angelo (2003): From 1D Chain to 3D
Network. Tuning Hybrid II-VI Nanostructures and Their Optical Properties. In Journal of the American
Chemical Society 125 (23), pp. 70497055. DOI: 10.1021/ja0343611.
20) Ki, Wooseok; Li, Jing (2008): A Semiconductor Bulk Material That Emits Direct White Light. In
Journal of the American Chemical Society 130 (26), pp. 81148115. DOI: 10.1021/ja801601y.
21) Xu, Feng; Wang, Hao; Teat, Simon J.; Liu, Wei; Xia, Qibin; Li, Zhong; Li, Jing (2015): Synthesis,
structure and enhanced photoluminescence properties of two robust, water stable calcium and magnesium
coordination networks. In Dalton Transactions 44 (47), pp. 2045920463.
22) Yam, Vivian Wing-Wah; Au, Vonika Ka-Man; Leung, Sammual Yu-Lut (2015): Light-Emitting Self-
Assembled Materials Based on d8 and d10 Transition Metal Complexes. In Chemical Reviews 115 (15),
pp. 75897728. DOI: 10.1021/acs.chemrev.5b00074.
23) Henline, Kylie M.; Wang, Charles; Pike, Robert D.; Ahern, John C.; Sousa, Bryer; Patterson, Howard
H. et al. (2014): Structure, Dynamics, and Photophysics in the Copper(I) IodideTetrahydrothiophene
System. In Crystal Growth & Design 14 (3), pp. 14491458. DOI: 10.1021/cg500005p.
24) Jiang, Dong-Ping; Yao, Ru-Xin; Ji, Fang; Zhang, Xian-Ming (2013): Cuprous Halide Coordination
Polymers Based on Cationic [Cu4X2] and [Cu3X] Clusters and [Cu2Br]n Layers with Tetrazolates as
Assembling Ligands. Highly Connected Networks and Halide-Dependent Luminescence. In Eur. J. Inorg.
Chem. 2013 (4), pp. 556562. DOI: 10.1002/ejic.201200949.
25) Khatri, Natasha M.; Pablico-Lansigan, Michele H.; Boncher, William L.; Mertzman, Julie E.;
Labatete, Aura C.; Grande, Laura M. et al. (2016): Luminescence and Nonlinear Optical Properties in
Copper(I) Halide Extended Networks. In Inorganic Chemistry 55 (21), pp. 1140811417. DOI:
10.1021/acs.inorgchem.6b01879.
26) Li, Shi-Li; Zhang, Fu-Qiang; Zhang, Xian-Ming (2015): An organic-ligand-free thermochromic
luminescent cuprous iodide trinuclear cluster. Evidence for cluster centered emission and configuration
distortion with temperature. In Chemical Communications 51 (38), pp. 80628065. DOI:
10.1039/C5CC01154J.
27) Benito, Quentin; Le Goff, Xavier F.; Nocton, Gregory; Fargues, Alexandre; Garcia, Alain; Berhault,
Aurlie et al. (2015): Geometry Flexibility of Copper Iodide Clusters. Variability in Luminescence
Thermochromism. In Inorganic Chemistry 54 (9), pp. 44834494. DOI: 10.1021/acs.inorgchem.5b00321.
28) Mentor et al. (2017): A mechanochemical route toward the rational, systematic, and cost-effective
green synthesis of strongly luminescent copper iodide based hybrid phosphors. In Journal of Materials
Chemistry C 5 (24), pp. 59625969. DOI: 10.1039/C7TC00889A.
29) Zhang, Xian-Ming; Hou, Juan-Juan; Guo, Cai-Hong; Li, Chun-Fang (2015): A New Class of Cuprous
Bromide Cluster-Based Hybrid Materials. Direct Observation of the Stepwise Replacement of Hydrogen
Bonds by Coordination Bonds. In Inorganic Chemistry 54 (2), pp. 554559. DOI: 10.1021/ic5024168.
30) Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth; Alarousu, Erkki; Burlakov,
Victor M.; Peng, Wei et al. (2015): High-quality bulk hybrid perovskite single crystals within minutes by
inverse temperature crystallization. In Nature Communications 6, p. 7586. DOI: 10.1038/ncomms8586.
31) Saparov, Bayrammurad; Mitzi, David B. (2016): OrganicInorganic Perovskites. Structural
Versatility for Functional Materials Design. In Chemical Reviews 116 (7), pp. 45584596. DOI:
10.1021/acs.chemrev.5b00715.
32) Yin, Jun; Li, Hong; Cortecchia, Daniele; Soci, Cesare; Brdas, Jean-Luc (2017): Excitonic and
Polaronic Properties of 2D Hybrid OrganicInorganic Perovskites. In ACS Energy Letters 2 (2), pp. 417
423. DOI: 10.1021/acsenergylett.6b00659.
33) Liu, Wei et al. (2017): A Systematic Approach to Achieving High Performance Hybrid Lighting
Phosphors with Excellent Thermaland Photostability. In Advanced Functional Materials.
34) Liu, Wei et al. (2015): A family of highly efficient CuI-based lighting phosphors prepared by a
systematic, bottom-up synthetic approach. In Journal of the American Chemical Society 137 (29),
pp. 94009408.
35) Zhang, Xiao; Mentor; Wei, George Z.; Banerjee, Debasis; Hu, Zhichao; Li, Jing (2014): Systematic
Approach in Designing Rare-Earth-Free Hybrid Semiconductor Phosphors for General Lighting
Applications. In J. Am. Chem. Soc. 136 (40), pp. 1423014236.
36) Liu, Wei et al. (2017): All-in-One. Achieving Robust, Strongly Luminescent and Highly Dispersible
Hybrid Materials by Combining Ionic and Coordinate Bonds in Molecular Crystals. In Journal of the
American Chemical Society 139 (27), pp. 92819290. DOI: 10.1021/jacs.7b04550.
37) Winter, Mark (2017): The periodic table of elements. CrystalMaker Software Ltd. Available online at
https://www.webelements.com/.
38) United States Department of Energy (2015): Photometric Testing of White-Tunable LED Luminaires.
With assistance of Pacific Northwest National Laboratory. Oak Ridge, TN (CALiPER, Report 23).
Available online at https://energy.gov/sites/prod/files/2016/01/f28/caliper_23_white-tunable-led-
luminaires.pdf.
39) Diagram created by Dr. Wei Liu.