Issue 16, 2006

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}n1, {[Cd(fcz)2Cl2]·CH3OH·2H2O}n2, {[Co(fcz)2Cl2]·2CH3OH}n3 and {[Cu(fcz)2Cl2]·2CH3OH}n4 (fcz = fluconazole: α-(2,4-difluorophenyl)-α-(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 1 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 3 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 × 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.

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

Supplementary files

Article information

Article type
Paper
Submitted
11 Oct 2005
Accepted
04 Jan 2006
First published
18 Jan 2006

Dalton Trans., 2006, 1972-1980

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

H. Han, Y. Song, H. Hou, Y. Fan and Y. Zhu, Dalton Trans., 2006, 1972 DOI: 10.1039/B514431K

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