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In this study, three excellent yellow emissive Cu(I) complexes were synthesized, namely [Cu2I2(bipy)(POP)2]·4CH2Cl2 (1), [Cu2Br2(bipy)(POP)2]·4CH2Cl2 (2), and [CuCl(bipy)(POP)]·CH2Cl2·CH3OH (3) [bipy = 4,4′-bipyridine, POP = bis(2-diphenylphosphino-phenyl)ether]. The synthesis and characterization of three complexes are introduced. Complexes 1–3 have luminescent emission peaks of 529–532 nm, belonging to yellow light emission, and their quantum yield is 72–88%. Complex 2 exhibits an exceptionally high quantum yield of 88% and its lifetime is 9.6 μs. Among the available data, this result is one of the best luminescence results for yellow luminescent cuprous complexes. This study enriches the understanding of the photophysical properties of Cu(I) complexes and offers new insights for the development of efficient OLED materials. [ABSTRACT FROM AUTHOR]

Herein, a series of ionic mononuclear Cu(I) complexes, [Cu(phen)(bdppmapy)]Cl (1a), [Cu(phen)(bdppmapy)]Br (2a), [Cu(phen)(bdppmapy)]I (3a), [Cu(phen)(bdppmapy)]SCN (4a), [Cu(Dpq)(bdppmapy)]Cl (1b), [Cu(Dpq)(bdppmapy)]Br (2b), [Cu(Dpq)(bdppmapy)]I (3b) and [Cu(Dpq)(bdppmapy)]SCN (4b) {phen = [1,10]phenanthroline; Dpq = pyrazino[2,3-f][1,10]-phenanthroline; bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine} have been synthesized and characterized by using IR, NMR, elemental analysis, single crystal X-ray diffraction analysis, fluorescence spectroscopy methods, and UV-vis and terahertz (THz) time-domain absorption spectroscopy. Their crystal structures were elucidated by X-ray crystallography and their photophysical properties were investigated in detail. All the above complexes exhibit a 1D to 3D supramolecular structure which is linked together by intermolecular weak interaction forces and hydrogen bonds. By regulating ligands and anions, the emission wavelengths of these complexes are quite different in the range from 533 nm to 604 nm. Theoretical calculations and photophysical properties indicate that luminescence is derived from metal-to-ligand charge transfer (MLCT) excited states. In the meantime, the results of calculations show that the stabilization of the increased conjugation of the ligand-based π* orbital is ascribed to the observed bathochromic-shift in the MLCT transitions. [ABSTRACT FROM AUTHOR]

The synthesis of four heteroleptic dinuclear Cu(I) complexes bearing tetraphosphine and diimine ligands was reported. Complexes 1–3 were successfully obtained through microwave synthesis while complex 4 was synthesized through traditionally stirring at room temperature. These complexes are listed as follows: [Cu2(Dpq)2(dppeda)](ClO4)2·1.5CH2Cl2 (1), [Cu2(neo)2(dppeda)](ClO4)2·1.3CH2Cl2·1.7C4H10O (2), [Cu2(batho)2(dppeda)](ClO4)2·C4H10O (3), and [Cu2(batho)2(dpppda)](ClO4)2·3CH2Cl2 (4) {(Dpq = pyrazino[2,3-f][1,10]phenanthroline, batho = 4,7-diphenyl-1,10-phenanthroline, neo = 2,9-dimethyl-1,10-phenanthroline, dppeda = N1,N1,N2,N2-tetrakis[(diphenylphosphino)methyl]-1,2-ethanediamine, and dpppda = N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamine}. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. Photophysical studies and time domain density functional theory (TD-DFT) calculations show that the luminescence performance of these four complexes is ascribed to metal-to-ligand charge transfer (MLCT) mixed with ligand-to-ligand charge transfer (LLCT), and complex 2 shows green emission at 574 nm with the highest quantum yield of up to 52.80%. In addition, the research of photoluminescence properties under the guidance of terahertz spectroscopy technology leads to the preliminary discovery of a correlation between crystal packing and luminescence. It is found that the terahertz spectrum and absorption peak are strongly interdependent on C–H⋯π and π⋯π interactions, and the external weak interactions have negative effects on the luminescence performance. Herein, we predict that the terahertz spectroscopy analysis establishes a bridge between weak interactions (C–H⋯π and π⋯π interactions) and the photoluminescence properties, and puts forward a problem that should be noticed in designing Cu(I) complexes. [ABSTRACT FROM AUTHOR]

Five mono-nuclear silver(I) complexes with the ligand 2,9-dimethyl-1,10-phenanthroline, namely [Ag(DPEphos)(dmp)]BF4 ( 1), [Ag(DPEphos)(dmp)]CF3SO3 ( 2), [Ag(DPEphos)(dmp)]ClO4 ( 3), [Ag(DPEphos)(dmp)]NO3 ( 4), and [Ag(dppb)(dmp)]NO3 ·CH3OH ( 5) {DPEphos = bis[2-(diphenylphosphanyl)phenyl]ether, dppb = 1,2-bis(diphenylphosphanyl)benzene, dmp = 2,9-dimethyl-1,10-phenanthroline} were characterized by X-ray diffraction, IR, 1H NMR, 31P NMR and fluorescence spectroscopy. Their terahertz (THz) time-domain spectra were also studied. In these complexes the silver(I), which is coordinated by two kinds of chelating ligands, adopts four-coordinate modes to generate mono-nuclear structures. In complexes 1, 3- 5, offset π ···π weak interactions exist between the neighboring benzene rings. In the 31P NMR spectra, there exist splitting signals (dd), which can be attributed to the coupling of the 107,109Ag-31P. All the emission peaks of these complexes are attributed to ligand-centered excited states. [ABSTRACT FROM AUTHOR]

Two series of Ln3+-coordination frameworks were synthesized by using positional isomers of naphthalenedisulfonate (Nds) ligands, along with oxalate (ox) and 1,10-phenanthroline (phen) ligands under the same experimental conditions, namely, {[Ln(1,5-Nds)0.5(ox)(phen)(H2O)]·H2O}n (Ln = Eu (1), La (2), and Sm (3)), [La(2,6-Nds)(ox)0.5(phen)2(H2O)]n (4) and [Ln(2,6-Nds)0.5(ox)(phen)(H2O)]n (Ln = Eu (5), Gd (6), and Tb (7)). Compounds 4 and 5–7 show different grid-like layers with a {63} topology based on [LaO5N4] and [LnO6N2] polyhedra as uninodal nodes, respectively. However, the 1,5-Nds-based linker can pillar into a high dimensionality pillared-layer microporous motif of complexes 1–3 with a {36·48·56·6} topology based on {LnO7N2} polyhedra as uninodal nodes, affording one-dimensional channels. Notably, highly luminescent microporous pillared-layer Eu3+-framework 1 is a promising luminescence sensor for small organic molecules and metal ions, especially for benzaldehyde and Fe3+. The luminescence behavior of 1 is affected by the solvents and the luminescence color changes from red-pink to blue. The possible luminescence sensing mechanism for Fe3+ and the effect of using different solvents on the luminescence sensing of metal ions were explored. It is noteworthy that complex 1 can be excited with a longer excitation wavelength (358 nm), which is an important requirement for applications. [ABSTRACT FROM AUTHOR]

A Cd(ii)-based metal–organic framework, [Cd2(DPDC)2(BTB)]∞ (Cd-MOF, DPDC = 2,2′-diphenyldicarboxylate and BTB = 1,4-bis(1,2,4-triazol-1-yl)butane) was successfully constructed via a hydrothermal reaction. Structural analysis shows that the synthesized Cd-MOF is a three-dimensional (3D) architecture crystallized in the hexagonal system with a chiral space group P61. Powder X-ray diffraction experiments and thermogravimetric analysis reveal that the constructed Cd-MOF has a high chemical and thermal stability. A study of additional mechanical properties indicates that it exhibits a moderate stiffness with the average values of Young's modulus (E) and H as 11.3(2) and 0.9(7) GPa, respectively. The luminescence properties of the Cd-MOF were further studied. The result shows that it could be an effective sensor to the organic nitrobenzene molecule via a strong quenching effect, and also to the inorganic Tb(iii) ion by a strong green emission effect. Moreover, when loading bimetal ions (Eu(iii) and Tb(iii)) into the Cd-MOF/methanol suspension, tunable visible luminescence can also be achieved by carefully adjusting the excitation wavelengths. [ABSTRACT FROM AUTHOR]

The hydrothermal reaction of the same reactive system containing Ln(NO3)3·6H2O, tetrafluorophthalic acid (H2TFPht), and 1,10-phenanthroline (phen) at different temperatures yielded coordination polymers, [Ln2(TFPht)3(phen)2(H2O)2]·H2O (Ln = Sm 1, Eu 2, Gd 3, Tb 4, Dy 5; at 120 °C), La(TFPht)(TFBA)(phen)(H2O) (6; at 160 °C), Ln3(TFPht)4(TFBA)(phen)3(H2O)3 (Ln = Dy 7, Tb 8, Yb 9; at 160 °C), and Ln2(TFBA)6(phen)2 (Ln = Eu 10, Tb 11; at 180 °C). 2,3,4,5-Tetrafluorobenzoic acid (TFBA) was produced from the decarboxylation of TFPht. X-ray structural analysis reveals that these compounds contain different structural motifs. Complexes 1–5 exhibit zigzag chain structures based on the center-related tetranuclear [Ln4] as SBUs (Secondary Building Units) with two crystallographically independent Ln3+ ions. Complex 6 contains a double chain structure with center-related binuclear [La2] as SBUs. Complexes 7–9 show single chain structures involving center-related hexanuclear [Ln6] as SBUs with three crystallographically independent Ln3+ ions. Complexes 10 and 11 have ribbon chain structures involving binuclear [Ln2] as SBUs with two crystallographically independent Ln3+ ions. The photoluminescence properties of complexes 1–5 were studied. The Eu3+ and Tb3+ complexes exhibit bright red and green emissions with quantum yields of 15.87% for 2 and 23.82% for 4. The two-component Dy:Eu- and three-component Gd:Dy,Eu-doped complexes provided white light emission. Moreover, 2 could be a potential luminescent probe for detecting nitrobenzene and Ni2+ ion through significant fluorescence decrease of Eu3+. [ABSTRACT FROM AUTHOR]

Different copper(I) complexes were synthesized by changing the anions and ligands. All complexes show 0D−3D structures which are caused by intermolecular interactions such as hydrogen bonds, C H⋯π interactions and π⋯π interactions. The luminescence properties of complexes are generated by metal-to-ligand charge transfer (MLCT). In addition, THz time-domain spectroscopy was also studied in this research. Nine novel copper(I) complexes with diphosphine and diimine ligands, namely [Cu(dpq)(xantphos)]BF 4 (1), [Cu(dpq)(xantphos)]I (2), [Cu(dpq)(dppp)]BF 4 (3), [Cu(dppz)(dppp)]BF 4 (4), [Cu(dppz)(dppp)]I (5), [Cu(dppz)(pop)]I (6), [Cu(dpq)(pop)]I (7), [Cu(dpq)(pop)]Br (8), [Cu(dpq)(pop)]SCN (9) (dpq = pyrazino[2,3-f][1,10]phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene, dppp = 1,3-bis(diphenylphosphino)propane, pop = 1,1′-[(Oxydi-2,1-phenylene)]bis[1,1-diphenylphosphine]), were characterized by single crystal X-ray diffraction, IR, elemental analysis, 1H NMR, 31P NMR, fluorescence spectra and terahertz time domain spectroscopy (THz-TDS). These nine complexes were synthesized by the reactions of copper salts, diimine ligands and various of P-donor ligands through one-pot method. Single crystal X-ray diffraction reveals that complex 9 is of a simple mono-nuclear structure while complexes 6 and 7 are of dimer structures. For complex 8 , hydrogen bonds and C H⋯π interactions lead to the formation of a 1D infinite chain structure. Interestingly, complexes 1 – 5 show novel 2D or 3D network structures through C H⋯π interactions. In addition, complexes 1 – 3 and 6 – 9 exhibit interesting fluorescence in the solid state at room temperature. Among the nine complexes, complex 1 shows the highest quantum yield up to 37% and the lifetime of 1 is 6.0 μs. The terahertz (THz) time-domain spectra of these complexes were also studied. [ABSTRACT FROM AUTHOR]

Graphical abstract Reactions of diphosphine and diimine ligands with AgCF 3 SO 3 under different reaction conditions gave rise to six complexes with different structures. The representative one-dimensional coordination polymer {[Ag(dppe)(dmp)](CF 3 SO 3)·(CH 3 OH)·(H 2 O)} n exhibited good stability and excellent catalytic activity toward the photodegradation of a spectrum of common organic dyes in water under UV light irradiation. Abstract Six new silver(I) complexes with diphosphine ligands and 1,10-phenanthroline derivatives are named by [Ag 2 (dppe)(dicnq) 2 ](CF 3 SO 3) 2 (1), [Ag 2 (dppp) 2 (dicnq) 2 ](CF 3 SO 3) 2 (2), [Ag 2 (dppb) 2 (dicnq) 2 ](CF 3 SO 3) 2 (3), [Ag(DPEphos)(dicnq)]CF 3 SO 3 (4), {[Ag(dppe)(dmp)](CF 3 SO 3)·(CH 3 OH)·(H 2 O)} n (5), [Ag 2 (dppp) 2 (dmp) 2 ](CF 3 SO 3) 2 ·(H 2 O) (6), (dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, dppb = 1,4-bis(diphenylphosphino)butane, DPEphos = bis[2-(diphenylphosphanyl)phenyl]ether, dmp = 2,9-dimethyl-1,10-phenanthroline, dicnq = 6,7-dicyanodipyridoquinoxaline) were characterized by IR and X-ray diffraction. Further fluorescence spectroscopy, photocatalytic properties and terahertz time-domain spectra (THz-TDS) were performed on 2 – 6. Complexes 1 – 3 and 6 were binuclear, while 4 was mononuclear. Complex 5 was a coordination polymer, displaying a one-dimensional infinite chain. Moreover, complexes 1 , 2 and 4 were assembled via several pairs of C H⋯π interactions to 1D–3D supramolecular architectures. The emission peaks of the complexes 2 – 4 all exhibit a large degree of red shift, which may be tentatively attributed to the intraligand transition. Compounds 2 – 6 represented the first examples of Ag(I) complexes bearing both diphosphine and diimine ligands that exhibit high, efficient photocatalytic abilities for dye degradation under UV light and show good stability toward photocatalysis. [ABSTRACT FROM AUTHOR]

Three metal-organic frameworks (MOFs), [M(dpdc)(btb) 0.5 ] n (M = Zn 1 , Cd 2 ; dpdc = 3,3′-diphenyldicarboxylate and btb = 1,4-bis(1,2,4-triazol-1-yl)butane) and [Cu 3 (dpdc) 3 (btb) 2 ] n ( 3 ) were prepared and structurally determined. 1 is a 2D structure with the topology of {3 3 ·4 7 ·5 4 ·6}, while 2 possesses a 3D framework with the {3 12 ·4 29 ·5 14 } topology. Complex 3 displays a 3D framework with the topology of {3 15 .4 35 .5 5 }2{3 6 .4 8 .5 12 .6.7}. 1 – 2 exhibit intense blue luminescence and high stability in water, which make them highly promising candidates as sensors using in aqueous medium. Complex 1 is a potential bi-functional chemosensor for Fe 3+ and Al 3+ ions while 2 displays a selective sensing ability to Fe 3+ ion. Quenching mechanism of Fe 3+ on the luminescence of 1 – 2 is attributed to the charge transfer process LMCT. 1 and 2 have same compositions but have different structures, thermally stabilities and different luminescence sensing functions. The relationship between MOF structures and luminescence sensing toward metal ions are further discussed. [ABSTRACT FROM AUTHOR]

Eight silver (I) complexes with P-donor ligands [triphenylphosphine (PPh 3 ), bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane(dppb)] and mercaptan ligands [3-amino-5-mercapto-1,2,4-triazole (H 2 AMTA), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT) and 2-mercapto-5-methyl-benzimidazole (HMMBD)] named by [Ag 2 (PPh 3 ) 4 (HAMTA) 2 ] n ( 1 ), [Ag 3 (dppm) 3 (AMTD) 2 ] 2 (BF 4 ) 2 ·(dppm) ( 2 ), [Ag 3 (dppm) 3 (AMTD) 2 ] 2 (ClO 4 ) 2 ·(dppm) ( 3 ), [Ag 4 (dppm) 4 (MNBT) 2 ](SO 4 )·(H 2 O) ( 4 ), [Ag 4 (dppe) 4 (HAMTA) 2 (AMTA)] ( 5 ), [Ag 2 (dppb) 2 (HAMTD) 2 ](CF 3 SO 3 ) 2 ·2(CH 3 OH) ( 6 ), [Ag 2 (dppb) 2 (HMNBT) 2 ](CF 3 SO 3 ) 2 ( 7 ) and {[Ag(dppb)(HMMBD) 2 ](CF 3 SO 3 )·2(CH 3 OH)·(H 2 O)} n ( 8 ) are characterized by X-ray diffraction, NMR and fluorescence spectroscopy. Complexes 1 and 8 show 2D network structure. Complexes 2 – 5 are multi-nuclear clusters. Complexes 6 – 7 are of di-nuclear structure. In complex 7 , the offset π⋯π interactions between the neighboring benzene rings help to form the 1-D infinite chain. All the emission peaks of these complexes are attributed to ligands-centered [π–π ∗ ] transitions. [ABSTRACT FROM AUTHOR]

Six different rare earth complexes were synthesized in acetonitrile. All these six complexes are of 1D infinite chain structure, and stacking mode analysis exhibit 3D network supramolecular structures which are formed through bridged L ligands and C H∙∙∙π interactions. The highest quantum yield of these complexes is up to 37% in solid state at room temperature. • Six novel lanthanide complexes were synthesized through a simple one-pot reaction. • They display 1D structures depending on geometry of bridging biphosphonate ligands. • Complexes 2 and 4 show characteristic emission peaks of Ln(III) with high luminescent quantum yields. Six novel lanthanide complexes [LnL(Phen)Cl 3 n (1 – 6) (Ln = Sm, Eu, Gd, Tb, Dy, Ho) (L = tetraethyl ethylenebisphosphonate, Phen = 1,10-phenanthroline) have been synthesized through a simple one-pot reaction. Complexes 1 – 6 are of 1D infinite chain structure. The C H∙∙∙π interactions and the bridging action of L ligand lead to the formation of 3D network structures for 1 – 6. Emission spectra of complexes 1, 2, 4 and 5 show characteristic emission peaks of Sm3+, Eu3+, Tb3+ and Dy3+, respectively. Quantum yield of 2 is up to 37% while that of 4 reaches 31% in solid state, so they can be used as potential luminescent materials. [ABSTRACT FROM AUTHOR]