TY - JOUR

T1 - Luminescent detection by coordination polymers derived from a pre-organized heterometallic carboxylic building unit

AU - Sapianik, Aleksandr A.

AU - Kiskin, Mikhail A.

AU - Samsonenko, Denis G.

AU - Ryadun, Alexey A.

AU - Dybtsev, Danil N.

AU - Fedin, Vladimir P.

PY - 2018/5/1

Y1 - 2018/5/1

N2 - A tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (piv− = pivalate, py = pyridine) could be viewed as an 8-connected node or a dimer of 3-connected binuclear {LiZn(RCOO)3} carboxylate complexes. A solvothermal reaction of c with biphenyldicarboxylic acid (H2bpdc) results in two layered MOFs [{LiZn}2(bpdc)3(dma)4]·3DMA·H2O (1a ⊃ DMA) and [{LiZn}2(bpdc)3(nmp)4]·4NMP (1b ⊃ NMP) in dimethylacetamide (DMA) or N-methyl-2-pyrrolidone (NMP) solvents, respectively. The reaction of [Li2Zn2(piv)6(py)2] with H2bpdc and diazabicyclo[2.2.2]octane (dabco) in dimethylformamide (DMF) affords a 3D MOF [Li2Zn2(bpdc)3(dabco)]·9DMF·4H2O (2 ⊃ DMF) with an open structure. The frameworks in 1a and 1b are based on 3-connected binuclear nodes, connected through linear bpdc2− anions into a twofold interwoven honeycomb (hcb) layers, packed in ABAB manner. The tetranuclear units in 2 are connected by both bpdc2− and dabco into a 3D non-interpenetrated net with body-centered cubic (bcu) topology. The solvent molecules in both 1 and 2 could be substituted to various aromatic species, which nature affects the photoluminescence properties of the framework in a different way. For example, the substitution to nitrobenzene completely quenches the luminescence while the inclusion of benzyl alcohol, anisole, acetophenone into porous channels of 2 results in a marked shift of the emission peak maxima as well as an enhancement of the quantum yields.

AB - A tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (piv− = pivalate, py = pyridine) could be viewed as an 8-connected node or a dimer of 3-connected binuclear {LiZn(RCOO)3} carboxylate complexes. A solvothermal reaction of c with biphenyldicarboxylic acid (H2bpdc) results in two layered MOFs [{LiZn}2(bpdc)3(dma)4]·3DMA·H2O (1a ⊃ DMA) and [{LiZn}2(bpdc)3(nmp)4]·4NMP (1b ⊃ NMP) in dimethylacetamide (DMA) or N-methyl-2-pyrrolidone (NMP) solvents, respectively. The reaction of [Li2Zn2(piv)6(py)2] with H2bpdc and diazabicyclo[2.2.2]octane (dabco) in dimethylformamide (DMF) affords a 3D MOF [Li2Zn2(bpdc)3(dabco)]·9DMF·4H2O (2 ⊃ DMF) with an open structure. The frameworks in 1a and 1b are based on 3-connected binuclear nodes, connected through linear bpdc2− anions into a twofold interwoven honeycomb (hcb) layers, packed in ABAB manner. The tetranuclear units in 2 are connected by both bpdc2− and dabco into a 3D non-interpenetrated net with body-centered cubic (bcu) topology. The solvent molecules in both 1 and 2 could be substituted to various aromatic species, which nature affects the photoluminescence properties of the framework in a different way. For example, the substitution to nitrobenzene completely quenches the luminescence while the inclusion of benzyl alcohol, anisole, acetophenone into porous channels of 2 results in a marked shift of the emission peak maxima as well as an enhancement of the quantum yields.

KW - Coordination polymers

KW - Crystal engineering

KW - Heterometallic complexes

KW - Luminescence

KW - Metal–organic framework

KW - RATIONAL SYNTHESIS

KW - EXPLOSIVES

KW - NETWORK

KW - COMPLEX

KW - PHOTOLUMINESCENCE

KW - MOF

KW - FRAMEWORKS

KW - Metal-organic framework

KW - METAL

KW - LIGAND

KW - POLYCATENATION

UR - http://www.scopus.com/inward/record.url?scp=85042356882&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2018.02.007

DO - 10.1016/j.poly.2018.02.007

M3 - Article

AN - SCOPUS:85042356882

VL - 145

SP - 147

EP - 153

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

ER -