Synthesis, Structural Characterisation, and Spectroscopic Properties of Copper(I) Complexes and their Applications to Dye-Sensitised Solar Cells

2015 ◽  
Vol 68 (7) ◽  
pp. 1144 ◽  
Author(s):  
Ting-Hong Huang ◽  
Jie Yan ◽  
Ye-Feng Liu ◽  
Yun-Tao Xie ◽  
Chen Jia
Keyword(s):  
Solar Cells ◽  
Charge Transfer ◽  
Spectroscopic Properties ◽  
Crystal Structure Analysis ◽  
Acetonitrile Solution ◽  
Structural Characterisation ◽  
Π Interactions ◽  
Ligand Charge Transfer ◽  
11B Nmr ◽  
Supramolecular Networks

Based on the ligand 1,4-bis(2-(diphenylphophino)benzylideneamino)benzene (pbb), two complexes, [Cu2(pbb)(2,2′-bipyridine)2](BF4)2 (1) and [Cu2(pbb)(phen)2](BF4)2 (2), have been prepared and characterised by IR, 1H NMR, 31P NMR, 19F NMR, and 11B NMR spectroscopy and X-ray crystal structure analysis. Structural analysis reveals that complexes 1 and 2 contain 1D infinite chains and 2D supramolecular networks constructed by C–H···π and π···π interactions, and an ordered-layer-lattice of BF4– is located between these 2D networks. The results show that C–H···π and π···π interactions play an important role in the formation of 2D supramolecular networks. The UV-vis absorption peaks of complexes 1 and 2 display intraligand charge transfer and metal to ligand charge transfer (MLCT) absorption. Complexes 1 and 2 display efficient luminescent emission assigned to MLCT excited states, and the maximum emissions of these complexes in acetonitrile solution are different from those of the solid-state samples. In addition, complexes 1 and 2 have been exploited as sensitisers in dye-sensitised solar cells, and efficiencies are also observed.

Syntheses, Structures, Characterisation, and Spectroscopic Properties of CuI and AgI Complexes with Extended C–H···π and π···π Interactions

2014 ◽  
Vol 67 (6) ◽  
pp. 887 ◽  
Author(s):  
Ting-Hong Huang ◽  
Min-Hua Zhang
Keyword(s):  
Charge Transfer ◽  
Room Temperature ◽  
Spectroscopic Properties ◽  
Acetonitrile Solution ◽  
Fluorescent Properties ◽  
Π Interactions ◽  
Π Stacking ◽  
Ligand Charge Transfer ◽  
The One ◽  
Stacking Patterns

Based on the ligands N,N′-bis(pyridin-2-ylmethylene)benzene-1,4-diamine (pmb) and N,N′-bis(pyridin-2-ylmethylene)biphenyl-4,4′-diamine (pmbb), the three compounds [Cu2(pmb) (PPh3)2(Cl)2] (1), [Cu2(pmbb)(CH3CN)2(PPh3)2](BF4)2·2DMF (2), and [Ag2(pmbb)(PPh3)2] (ClO4)2 (3) have been synthesised and characterised. Structural analysis reveals that all of these complexes contain 1D supramolecular arrays, with different variations in π-stacking patterns and intermolecular C–H···π interactions. Crystal structures of 1 and 2 contain 1D tape-like arrays formed by C–H···π and π···π interactions, and an ordered-layer-lattice of DMF and BF4– in 2 is located between the one-dimensional array. For 3, π-stacking interactions lead to the construction of 1D supramolecular arrays and a 2D network. The results indicate that C–H···π and π···π interactions play an important role in the construction of the supramolecular structure. In addition, the absorption peaks of complexes 1 and 3 in the solid state at room temperature show intraligand charge transfer and metal-to-ligand charge transfer absorptions. The optical and fluorescent properties of 2 were also studied in acetonitrile solution at room temperature.

scholarly journals Theoretical Insight into the Spectral Characteristics of Fe(II)-Based Complexes for Dye-Sensitized Solar Cells—Part I: Polypyridyl Ancillary Ligands

2011 ◽  
Vol 2011 ◽  
pp. 1-11 ◽  
Author(s):  
Xiaoqing Lu ◽  
Shuxian Wei ◽  
Chi-Man Lawrence Wu ◽  
Ning Ding ◽  
Shaoren Li ◽  
...  
Keyword(s):  
Solar Cells ◽  
Charge Transfer ◽  
Optical Absorption ◽  
Absorption Spectra ◽  
Dye Sensitized Solar Cells ◽  
Optical Absorption Spectra ◽  
Ancillary Ligands ◽  
Dye Sensitized ◽  
Ligand Charge Transfer ◽  
Sensitized Solar Cells

The design of light-absorbent dyes with cheaper, safer, and more sustainable materials is one of the key issues for the future development of dye-sensitized solar cells (DSSCs). We report herein a theoretical investigation on a series of polypyridyl Fe(II)-based complexes of FeL2(SCN)2, [FeL3]2+, [FeL′(SCN)3]-, [FeL′2]2+, and FeL′′(SCN)2(L = 2,2′-bipyridyl-4,4′-dicarboxylic acid, L′ = 2,2′,2″-terpyridyl-4,4′,4″-tricarboxylic acid, L″= 4,4‴-dimethyl-2,2′ : 6′,2″ :6″,2‴-quaterpyridyl-4′,4″-biscarboxylic acid) by density functional theory (DFT) and time-dependent DFT (TD-DFT). Molecular geometries, electronic structures, and optical absorption spectra are predicted in both the gas phase and methyl cyanide (MeCN) solution. Our results show that polypyridyl Fe(II)-based complexes display multitransition characters of Fe → polypyridine metal-to-ligand charge transfer and ligand-to-ligand charge transfer in the range of 350–800 nm. Structural optimizations by choosing different polypyridyl ancillary ligands lead to alterations of the molecular orbital energies, oscillator strength, and spectral response range. Compared with Ru(II) sensitizers, Fe(II)-based complexes show similar characteristics and improving trend of optical absorption spectra along with the introduction of different polypyridyl ancillary ligands.

scholarly journals Light driven isomerization of coordinated ligand and modulation offac-[Re(CO)3(phen)(trans-bpe)]PF6photoluminescence in rigid media

2001 ◽  
Vol 3 (3) ◽  
pp. 143-164 ◽  
Author(s):  
Melina Kayoko Itokazu ◽  
André Sarto Polo ◽  
Neyde Yukie Murakami Iha
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Photophysical Properties ◽  
Acetonitrile Solution ◽  
Solid Films ◽  
Spectral Changes ◽  
Rhenium Complex ◽  
Photostationary State ◽  
Ligand Charge Transfer ◽  
Enhanced Luminescence

The excited state reactivity and photophysical properties offac-[Re(CO)3(phen)(L)]PF6(phen = 1,10-phenanthroline, L =trans- orcis-1,2-bis(4-pyridyl)ethylene, bpe) in PMMA (poly(methyl methacrylate)) films have been investigated and compared with those in acetonitrile solution.313 or 365 nm irradiation of the rhenium complex in PMMA leads to UV-vis spectral changes due to thetrans→cisisomerization of the coordinated bpe ligand. Thefac-[Re(CO)3(phen)(cis-bpe)]+product presents a markedly enhanced luminescence due to a lower lying metal-to-ligand charge transfer (MLCT) excited state in thecisisomer. This emitting property can be conveniently applied as a probe or sensor.Thecisis omer ratio in the photostationary state (PSS) is substantially smaller in solid films than in solution. The photochemical behavior of the freetrans-1,2-bis(4-pyridyl)ethylene in PMMA is also reported to establish comparisons with the investigation carried out in acetonitrile solution as well as with the behavior of the coordinated ligand.

Synthesis, Structural Characterisation, DFT Studies, and Spectroscopic Properties of Copper(I) Complexes with Extended C–H⋅⋅⋅π Interactions

2016 ◽  
Vol 69 (8) ◽  
pp. 826 ◽  
Author(s):  
Ting-Hong Huang ◽  
Jia-Qin Liu ◽  
Hu Yang ◽  
Bin Zhao ◽  
Jianping Shang
Keyword(s):  
Structural Analysis ◽  
Density Of States ◽  
Emission Spectra ◽  
Spectroscopic Properties ◽  
Partial Density ◽  
Energy Bands ◽  
Structural Characterisation ◽  
Π Interactions ◽  
Vis Spectroscopy ◽  
Crystal Structural

Two new CuI compexes, [Cu(phen)(PPh2(o-C6H4CHO))2](BF4)2 (1) and [Cu2(4,4′-bipy)(phen)2(PPh2(o-C6H4CHO))2](BF4)2·2CH3CN (2) (4,4′-bipy = 4,4′-bipyridine, PPh2(o-C6H4CHO) = o-(diphenylphosphino)benzaldehyde), have been synthesised and characterised by IR and UV-vis spectroscopy and X-ray crystal structural analysis. Structural analysis shows that the crystal structure of 1 contains 1D infinite chains formed by intermolecular C–H⋯π interactions, and the ordered-layer-lattice BF4– are located between the chains. For 2, intermolecular C–H⋯π and π⋯π interactions lead to the construction of 1D supramolecular arrays and 2D networks, and the ordered-layer-lattice CH3CN and BF4– are located between these networks. Density of states (DOS) and partial density of states (PDOS) studies indicate that the constitution of energy bands might be related to the change of ligands, with PPh2(o-C6H4CHO) showing the largest contributions to the HOMO of 2 and LUMO of 1. The UV-vis absorption spectra of 1 and 2 reveal that the absorption spectrum of 2 is red-shifted compared with 1. Moreover, the emission spectra of 1 and 2 in acetonitrile are also observed in the region of 480–700 nm.

Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Exchange ◽  
Ligand Substitution ◽  
Bidentate Ligand ◽  
The Other ◽  
Ligand Exchange Reaction ◽  
Multiple Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>

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