A series of metal–organic polymers assembled from MCl₂(M = Zn, Cd, Co, Cu): structures, third-order nonlinear optical and fluorescent properties

Abstract

In this paper four metal-organic polymers {[Zn(fcz)Cl2].CH3OH}n 1, {[Cd(fcz)2Cl2].CH3OH.2H2O}n 2, {[Co(fcz)2Cl2].2CH3OH}n 3 and {[Cu(fcz)2Cl2].2CH3OH}n 4 (fcz = fluconazole: alpha-(2,4-difluorophenyl)-alpha-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol) were synthesized and characterized by X-ray single crystal diffraction. Polymer consists of 1-D infinite chains arranged along the b-axis. All of polymers 2-4 exhibit a 2-D rhombohedral grid structure. We study the third-order nonlinear optical properties of fcz and polymers 1-4 in DMF solution by using 8 ns laser pulses at 532 nm, and find that 1 and 4 exhibit different NLO properties from fcz and both 2 and 3 show similar NLO properties to fcz. 1 possesses strong NLO refractive effects and large NLO absorptive behaviors. 2, 3 and fcz exhibit strong refractive effects, but their NLO absorptive behaviors are weaker than that of 1. The NLO effects of 4 are very weak. The study of optical limiting (OL) effects by using 40 ps laser pulses at 532 nm shows that fcz and polymer 3 possess a strong OL effect. The optical limiting threshold values of 0.15 J cm(-2) for fcz and 0.16 J cm(-2) for are comparable to those of many heterothiometallate clusters. Polymers 1, 2 and 4 show a weak OL effect. The fluorescent spectra in DMF solution (concentration: 1 x 10(-4) mol dm(-3)) show that polymers 1-4 exhibit different luminescence properties from fcz. The maximum wavelength of polymers 1-3 are blue shifted gradually by 2-12 nm while polymer 4 exhibits a fluorescent self-quenching phenomenon. These results demonstrate that metal ions play an important part in the NLO and fluorescent properties of coordination polymers.

Syntheses, crystal structures of a series of copper(II) complexes and their catalytic activities in the green oxidative coupling of 2,6-dimethylphenol

“…The crystal structures of complexes 5 and 6 have been described in our previous reports [17,18]. As shown in Scheme 1, complex 5 exhibits a 1D double-chain structure similar to that of complex 4.…”

“…With sulfate as the counterion, the 1D double chains coordination polymer 5 was obtained [17]. With chlorine as the counterion, the 2D network of complex 6 was formed [18]. Here, we chose nitrate as the counterion and synthesized a new 1D double chains coordination polymer 4 through the self-assembly of fcz ligand and copper ions.…”

“…for C 31 H 45 CuF 4-N 13 O 12 S: C,38.61;H,4.67;N,18.89. Found: C,38.52;H,4.67;N,18 ,3.95;N,20.72. Found: C,41.49;H,3.90;N,20.74%.…”

Two New 2-Benzoylbenzoate Metal Complexes with Bapen: Synthesis, Spectroscopic and Crystal Structures

“…Metal-organic frameworks exhibit interesting properties, and their enormous potential applications in supramolecular chemistry, catalysis, linear and nonlinear optics, gas separation, photoluminescence and molecular recognition, separation processes, ion exchange, and optoelectronics [1][2][3][4][5][6][7][8][9][10][11][12]. Carboxylato groups including ligands have versatile coordination mode: monodentate, chelate, different types of CO 2 bridges and O monoatomic bridges [13].…”

Supramolecular cobalt(II) complexes: syntheses, crystal structures and solvent effects

“…The development of new metal-organic complexes can provide new topologies for functional materials, in which pore size, coordination forms and functionality are all important variables [2]. Supramolecular complexes in which the metal centers are bridged through organic ligands are of much current interest, because of their enormous variety of structural topologies and as well as their potential applications in optoelectronics, magnetism and catalysis [3][4][5][6][7][8][9][10]. This subject is currently being pursued in our research, including the use of functional oxime groups and study of the magnetic, photoelectric and catalytic properties of such complexes.…”