TY - JOUR
T1 - Near-White Light Emission from Lead(II) Metal-Organic Frameworks
AU - Peedikakkal, Abdul Malik P.
AU - Quah, Hong Sheng
AU - Chia, Stacey
AU - Jalilov, Almaz S.
AU - Shaikh, Abdul Rajjak
AU - Al-Mohsin, Hasan Ali
AU - Yadava, Khushboo
AU - Ji, Wei
AU - Vittal, Jagadese J.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/9/17
Y1 - 2018/9/17
N2 - Reaction of bpy (bpy = 4,4′-bipyridine) with Pb(OAc)2·3H2O in DMF (DMF = dimethylformamide) afforded a metal-organic framework (MOF), [Pb2(μ-bpy)(μ-O2CCH3)2(μ-O2CCH3)2]·H2O (1). Reaction of bpy with Pb(O2CCF3)2 in a methanol and chloroform mixture furnished another MOF, [Pb(μ-bpy)(μ-O2CCF3)2]·1/2CHCl3 (2). However, the reaction of bpy with Pb(OAc)2·3H2O in the presence of trifluoroacetic acid in a similar reaction condition yielded a hydrogen-bonded zwitter-ionic complex of Pb(II), [Pb(bpy-H)2(O2CCF3)4] (3). All compounds have been characterized by single crystal X-ray crystallography, FT-IR, and 1H NMR spectroscopies. Compound 1 forms four heptacoordinated Pb(II) joined by (OCCH3)-O- linkages, resulting in a 3D noninterpenetrated MOF net with a four-connected uninodal sra (SrAl2) topology. However, in 2, tetra-connected Pb4(O2CCF3)8 cluster units are linked further through eight bpy ligands to furnish a doubly interpenetrated MOF with a new topology but having the very similar connectivity of 1, whereas 3 forms a zigzag hydrogen-bonded chain structure. The variation of carboxylate anions, pH of the reaction medium, and the ratio of the reactants profoundly affected the final topological structure of the compounds synthesized. The solid-state photoluminescence of 1-3 was investigated at room temperature. Interestingly 1, 2, and 3 achieved close to white light emission when excited at 329, 376, and 330 nm, respectively. The systematic understanding of the photophysical properties of analogous Pb-based compounds may open new perspectives for developing single-phase white-light-emitting materials using Pb(II) based MOFs.
AB - Reaction of bpy (bpy = 4,4′-bipyridine) with Pb(OAc)2·3H2O in DMF (DMF = dimethylformamide) afforded a metal-organic framework (MOF), [Pb2(μ-bpy)(μ-O2CCH3)2(μ-O2CCH3)2]·H2O (1). Reaction of bpy with Pb(O2CCF3)2 in a methanol and chloroform mixture furnished another MOF, [Pb(μ-bpy)(μ-O2CCF3)2]·1/2CHCl3 (2). However, the reaction of bpy with Pb(OAc)2·3H2O in the presence of trifluoroacetic acid in a similar reaction condition yielded a hydrogen-bonded zwitter-ionic complex of Pb(II), [Pb(bpy-H)2(O2CCF3)4] (3). All compounds have been characterized by single crystal X-ray crystallography, FT-IR, and 1H NMR spectroscopies. Compound 1 forms four heptacoordinated Pb(II) joined by (OCCH3)-O- linkages, resulting in a 3D noninterpenetrated MOF net with a four-connected uninodal sra (SrAl2) topology. However, in 2, tetra-connected Pb4(O2CCF3)8 cluster units are linked further through eight bpy ligands to furnish a doubly interpenetrated MOF with a new topology but having the very similar connectivity of 1, whereas 3 forms a zigzag hydrogen-bonded chain structure. The variation of carboxylate anions, pH of the reaction medium, and the ratio of the reactants profoundly affected the final topological structure of the compounds synthesized. The solid-state photoluminescence of 1-3 was investigated at room temperature. Interestingly 1, 2, and 3 achieved close to white light emission when excited at 329, 376, and 330 nm, respectively. The systematic understanding of the photophysical properties of analogous Pb-based compounds may open new perspectives for developing single-phase white-light-emitting materials using Pb(II) based MOFs.
UR - http://www.scopus.com/inward/record.url?scp=85052849591&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b00637
DO - 10.1021/acs.inorgchem.8b00637
M3 - Article
C2 - 30156408
AN - SCOPUS:85052849591
SN - 0020-1669
VL - 57
SP - 11341
EP - 11348
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -