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.

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.

Self-assembly of a Novel Three-dimensional Silver(I) Supramolecular Framework from Cationic Chains and Anionic Sheets

2010 ◽  
Vol 65 (2) ◽  
pp. 152-156
Author(s):  
Di Sun ◽  
Cheng-Feng Yang ◽  
Zhan-Hua Wei ◽  
Geng-Geng Luo ◽  
Na Zhang ◽  
...  
Keyword(s):  
Thermal Properties ◽  
Hydrogen Bonds ◽  
Self Assembly ◽  
Room Temperature ◽  
Three Dimensional ◽  
Supramolecular Framework ◽  
Π Interactions ◽  
Π Stacking ◽  
Benzenedicarboxylic Acid

A new three-dimensional (3D) supramolecular framework, [Ag2(bipy)2(bdc)·4H2O]n 1, has been synthesized by the ultrasonic reaction of Ag2O, bipy and H2bdc (H2bdc = 1,4-benzenedicarboxylic acid; bipy = 4,4’-bipyridine) at room temperature. It exhibits a new 3D supramolecular framework which is built from cationic Ag-bipy chains and anionic bdc-H2O sheets through hydrogen bonds, π · · ·π stacking and C-H· · ·π interactions. Additionally, the photoluminescent and thermal properties of 1 were investigated.

π-π Interactions between Pyrylium and Phenyl Rings in the Crystal

1997 ◽  
Vol 52 (4) ◽  
pp. 485-489 ◽  
Author(s):  
Teodor Silviu Balaban ◽  
Nina G. Furmanova
Keyword(s):  
Charge Transfer ◽  
Crystal Structures ◽  
Crystallographic Axis ◽  
Π Interactions ◽  
Charge Transfer Interaction ◽  
Π Stacking ◽  
Phenyl Rings ◽  
A Charge

Abstract The crystal structures of two isomeric phenyl-substituted pyrylium perchlorates, 2,6-di-methyl-4-phenylpyrylium (1) and 2,4-dim ethyl-6-phenylpyrylium (2), have been determined. Both cations are planar in the crystal so that the electron deficient pyrylium rings can interact strongly with the phenyl rings of adjacent molecules forming stacks along the shortest crystallographic axis. The phenyl rings may act as donors in a charge transfer interaction which is more pronounced in 1 than in 2. Charge transfer appears as a non-mandatory consequence of the π-π stacking. The structures demonstrate the electrostatic nature of these interactions conforming to the model of Hunter and Sanders [ 1 ].

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.

Donor/Akzeptor-Komplexe aus 1,3,5-Tris(dimethylamino)benzol und 1,2,3,4,5,6-Hexacyanobenzol/Donor/Acceptor Complexes from 1,3,5-Tris(dimethylamino)benzene with 1,2,3,4,5,6-Hexacyanobenzene

1989 ◽  
Vol 44 (3) ◽  
pp. 327-332 ◽  
Author(s):  
◽  
R. Niebl ◽  
G. Renner ◽  
D. von der Ruhr ◽  
A. K. Kilic ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Single Crystal ◽  
Room Temperature ◽  
Charge Transfer Complex ◽  
Acetonitrile Solution ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystallization Method ◽  
Donor Acceptor

Reaction of 1,3,5-tris(dimethylamino)benzene (TDMAB ) with 1,2,3,4,5,6-hexacyanobenzene (HCNB) in acetonitrile solution gives - depending on the crystallization method - two different products: dark needles of a 1:1 (1) and black compact crystals with a metallic lustre of a 2:1 (2) charge transfer complex. 2 crystallizes in the triclinic space group P1 , Z = 1, a = 9.9489(22), b = 10.0555(21), c = 10.1418(20) Å , α = 115.006(16)°, β = 102.820(17)°, γ = 93.647(18)°, V = 882.3 Å3, dc = 1.2 g cm-3, measured at room temperature, R = 0.053 for 2670 observed independent reflections and 301 parameters. The structure contains isolated “trimers” of one HCNB acceptor which is “pancaked” by two TDMAB neighbors. The arrangement of these trimers in the lattice results in alternating HCNB and TDMAB sheets. The solid is diamagnetic.1 could not be obtained in crystals suitable for a single crystal X-ray investigation. Its paramagnetism which is observed immediately after preparation disappears in the course of several days.

Synthesis and Photophysical Properties of New Three-Coordinate N-Heterocyclic Carbene Copper Complex

2016 ◽  
Vol 878 ◽  
pp. 18-21
Author(s):  
Shao Bo Liu ◽  
Cheng Yi ◽  
Hong Ying Xia ◽  
Feng Zhao
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Absorption Band ◽  
Energy Absorption ◽  
Copper Complex ◽  
Room Temperature ◽  
Photophysical Properties ◽  
Emission Spectrometry ◽  
Emission Maximum ◽  
Ligand Charge Transfer

A three-coordinateopper (I) complex supported by N-heterocyclic carbene (NHC) ligand and bis [2-(diphenylphosphino) phenyl] ether (POP) ligand were successfully reported and characterized. The corresponding photophysical properties were investigated using UV-vis and emission spectrometry. The lowest-energy absorption band at 343 nm was assigned to metal-to-ligand charge transfer (MLCT) transtion. The emission maximum located at 470 nm upon excitation at 290 nm in PMMA films at room temperature originates from the typical 3MLCT excited state.

Synthesis and Spectroscopic Properties of 1,2-Diiminetricarbonylrhenium( I)chloride Complexes with Aliphatic Diimines (or 1,4-Diaza-1,3-butadienes) as Ligands

1999 ◽  
Vol 54 (3) ◽  
pp. 341-344 ◽  
Author(s):  
Markus Leirer ◽  
Günther Knör ◽  
Amd Vogler
Keyword(s):  
Excited State ◽  
Room Temperature ◽  
Spectroscopic Properties ◽  
Visible Spectral Region ◽  
Partial Charge ◽  
Bidentate Ligands ◽  
Charge Redistribution ◽  
Chloride Complexes ◽  
Diimine Ligands ◽  
Ligand Charge Transfer

Re(1,2-diimine)(CO)3Cl complexes with the aliphatic bidentate ligands diiminosuccinodinitrile (DISN), benzilbisanile (BEAN), bisacetylbisanile (BABA), and benzildiimine (BEDIM) are reported. The compounds show Re(I) to π*(diimine) metal-to-ligand charge transfer (MLCT) absorptions in the visible spectral region. The energy of these MLCT-transitions decreases in the series BABA > BEDIM > BEAN > DISN, depending on the π* acceptor properties of the coordinated diimine ligands. The maxima of these CT bands undergo a solvent-dependent shift (negative solvatochromism), which indicates a partial charge redistribution in the excited state. The compounds are not photoluminescent at room temperature and 77 K.

Synthesis and photophysical properties of naphthyl-, phenanthryl-, and pyrenyl-appended bis(pyridyl)triazine ligands and their Zn(II) and Ru(II) complexes1

2009 ◽  
Vol 87 (1) ◽  
pp. 254-263 ◽  
Author(s):  
Francesco Nastasi ◽  
Frédérique Loiseau ◽  
Sebastiano Campagna ◽  
Elaine A Medlycott ◽  
Marie-Pierre Santoni ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Absorption Spectra ◽  
Room Temperature ◽  
Photophysical Properties ◽  
Fluid Solution ◽  
Aromatic Rings ◽  
Aryl Group ◽  
Strong Emission ◽  
Ligand Charge Transfer ◽  
Rigid Matrix

A family made of four bis(pyridyl)triazine ligands with appended aryl rings, including three fused aromatic rings, have been synthesized, and their corresponding homoleptic Ru(II) and Zn(II) complexes have been prepared and characterized by several means. The free ligands 2,4-di(2-pyridyl)-6-phenyl-1,3,5-triazine (L1); 2,4-di(2-pyridyl)-6-(1-naphthyl)-1,3,5-triazine (L2); 2,4-di(2-pyridyl)-6-(9-phenanthryl)-1,3,5-triazine (L3); and 2,4-di(2-pyridyl)-6-(1-pyrenyl)-1,3,5-triazine (L4) were formed in triazine ring-forming reactions from the reactions of the cyano-functionalized aromatic rings with LiNMe2 followed by the addition of 2 equiv. of 2-cyanopyridine. The metal complexes examined in this study are the homoleptic Ru(II) complexes Ru(L1)22+ (2a), Ru(L2)22+ (2b), Ru(L3)22+ (2c), and Ru(L4)22+ (2d) and Zn(II) complexes Zn(L1)22+ (3a), Zn(L2)22+ (3b), Zn(L3)22+ (3c), and Zn(L4)22+ (3d). Also, crystallographic data for the free ligands and Zn(II) and Ru(II) complexes have been obtained in some cases. The redox behaviour and absorption spectra of all the species have been investigated, together with the luminescence properties of the free ligands at room temperature in fluid solution and of the Ru(II) complexes both at room temperature in fluid solution and at 77 K in rigid matrix. The redox data indicate that the free ligands are reduced twice at relatively mild potentials (< –2.30 V vs. SCE), with the first reduction almost independent of the nature of the substituted aryl group. The UV absorption spectra of all the compounds are dominated by intense spin-allowed π–π* transitions mainly centered on the bis(pyridyl)triazine moiety; however, in L2–L4, moderately intense intraligand charge-transfer (ILCT) bands are also present. Such bands are red-shifted in the Zn(II) compounds, while they are obscured in the Ru(II) species by the more intense spin-allowed metal-to-ligand charge-transfer (MLCT) bands. The free ligands exhibit interesting emission properties, ranging from fluorescence from π–π* states to excimeric (in L4) and ILCT (in L2 and L3) emission. In the Ru(II) complexes, strong emission is found at 77 K from triplet MLCT states. For 2c and 2d, the emissive MLCT states are mixed with low-lying triplet ligand-centered states.Key words: triazine ligands, ruthenium complexes, zinc complexes, ILCT emission.

Polyoxometalate-based room-temperature phosphorescent materials induced by anion–π interactions

2020 ◽  
Vol 49 (11) ◽  
pp. 3408-3412 ◽  
Author(s):  
Xiao-Yuan Wu ◽  
Hai-Long Zhang ◽  
Sa-Sa Wang ◽  
Weiming Wu ◽  
Lang Lin ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Room Temperature ◽  
Room Temperature Phosphorescence ◽  
Π Interactions ◽  
Intermolecular Charge Transfer

A series of polyoxometalate-based host–guest materials emit strong red room-temperature phosphorescence attributed to intermolecular charge-transfer states which was caused by unorthodox anion–π interactions.

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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