Synthesis, Structure and Fluorescent Property of Indium-based Bimetallic Metal-organic Frameworks†

doi:10.7503/cjcu20180269

Abstract

Abstract:

Two mixed-metal coordination polymers, [In(OH)Cu(TBA)₂(C₂H₆OH)]·NMF(1) and [In_0.5Cd_0.5(TBA)(CH₃OH)][NO₃]_0.5·2NMF(2)[H₂TBA=4-(1H-tetrazol-5-yl)-benzoic acid, NMF=N-methylformamide], were synthesized under solvothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and single crystal X-ray diffraction. Complex 1 has a neutral 3D framework formed from the infinite chains and four-coordinated mononuclear Cu by TBA ligands. Compared to complex 1, In and Cd centers in complex 2 have the same infinite chains, which are bridged by TBA ligands to produce a cationic 3D structure. Complex 1 possesses a (4,4,8)-connected new topology while complex 2 belongs to (4,8)-connected topology. Notably, complex 2 can be used to detect Li⁺ and Fe³⁺ through either fluorescence enhancement or quenching effect, respectively. Thus complex 2 may be considered as a potential luminescent probe for the detection of Li⁺ and Fe³⁺.

Key words: Solvothermal synthesis method, Bimetallic system, Coordination polymer, Crystal structure, Fluorescent property

CLC Number:

O614

TrendMD:

WANG Dongmei,LIU Zihua,LI Guanghua,LIU Yunling,LI Chunxia. Synthesis, Structure and Fluorescent Property of Indium-based Bimetallic Metal-organic Frameworks^†[J]. Chem. J. Chinese Universities, 2018, 39(9): 1886.

Figures/Tables 7

Fig.1 Multiple SBUs consisting of ligand and metal cores(A), polyhedral view(B), ball and stick view(C) and the new topology type(D) of complex 1

Table 1 Crystal data and structural refinement for complexes 1 and 2

Complex	1
Empirical formula	C₂₁H₂₂CuInN₉O₇	C₁₃H₁₈Cd_0.5In_0.5N_6.5O_6.5
Formula weight	690.84	482.95
Temperature/K	293(2)	293(2)
Crystal system	Orthorhombic	Orthorhombic
Space group	Pmma	Imma
a/nm	0.72059(14)	1.8826(4)
b/nm	1.8500(4)	0.73469(15)
c/nm	1.5380(3)	1.5903(3)
α/(°)	90	90
β/(°)	90	90
γ/(°)	90	90
V/nm³	2.0503(7)	2.1996(8)
Z	2	4
D_c/(Mg·m^-3)	1.119	1.074
μ/mm^-1	1.361	0.971
F(000)	690	968
Reflections collected/Unique(R_int)	19273/2614(0.0695)	5518/1101(0.0193)
Goodness-of-fit on F²	1.093	1.127
R₁, wR₂[I>2σ(I)]^*	0.0402, 0.1263	0.0249, 0.0701
R₁, wR₂(all data)^*	0.0529, 0.1329	0.0301, 0.0725

Fig.2 Multiple SBUs consisting of ligand and metal cores(A), polyhedral view(B), ball and stick view(C) and new topology type(D) of complex 2

Fig.3 Simulated(a) and as-synthesized(b) powder X-ray diffraction(PXRD) patterns of complexes 1(A) and 2(B)

Fig.4 TG curves of complexes 1(A) and 2(B)

Fig.5 Wide-angle XRD(WAXRD) patterns of complexes 1(A) and 2 (B) after being heated up to 500 ℃

Fig.6 Solid-state emission spectra of H2TBA and complexes 1, 2(A), fluoresence intensity changes of complex 2 in different volatile organic solvents(B) and after addition of different metal ions(C) and linear plot of fluorescence intensity of complex 2 in DMF upon addition of Fe3+(D)

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