Nanocage-Based Tb³⁺-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO₂ with Epoxides and Knoevenagel Condensation

The catalytic performance of metal–organic framework (MOF)-based catalysts can be enhanced by increasing their catalytic sites, which prompts us to explore the multicore cluster-based skeletons by using designed functional ligands. Herein, the exquisite combination of [Tb4(μ2–OH)2(CO2)8] cluster and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) ligand generated a highly robust nanoporous framework of {[Tb4(BDCP)2(μ2–OH)2]·3DMF·5H2O}n (NUC-58), in which each four {Tb4} clusters are woven together to generate an elliptical nanocage (aperature ca. 12.4 Å). As far as we know, NUC-58 is an excellent nanocage-cluster-based {Tb4}-organic framework with the outstanding confined pore environments of a large specific surface area, high porosity, and plentiful coexisting Lewis acid–base sites of Tb3+, μ2–OH and Npyridine atoms. Performed experiments exhibited that NUC-58 owns a better catalytic performance for the cycloaddition reactions under mild conditions with a high turnover number and turnover frequency. Furthermore, NUC-58, as an eminent heterogeneous catalyst, can enormously boost the Knoevenagel condensation reactions. Thus, this work opens a path for the precise design of polynuclear metal cluster-based MOFs with excellent catalysis, stability, and regenerative behavior

Robust Nitro-Functionalized {Zn₃}‑Organic Framework for Excellent Catalytic Performance on Cycloaddition Reaction of CO₂ with Epoxides and Knoevenagel Condensation

Adjusting the Lewis acid–base sites in MOF-based catalysts to meet the demand for catalytic CO2 chemical fixation is a huge challenge. Herein, a highly robust rectilinear {Zn3}-based metal–organic framework of {[Zn3(TNTNB)2(4,4′-bip)(H2O)2]·5DMF·9H2O}n (NUC-80) was generalized from the solvothermal condition (H3TNTNB = 1,3,5-tri(3-nitro-4-carboxyphenyl)-2,4,6-trinitrobenzene, 4,4′-bip = 4,4′-bipyridine). Activated NUC-80a not only owns the large void volume (58%) and two kinds of solvent-accessible channels: rhombic-like (ca. 14.24 × 14.57 Å) along a axis and rectangular-like (ca. 11.72 × 14.48 Å) along b axis, but also is functionalized by rich metal sites and plentiful nitro groups on its inner surface. Performed catalytic experiments confirmed that NUC-80a could efficiently catalyze the cycloaddition reaction of CO2 with epoxides and Knoevenagel condensations of aldehydes and malononitrile under mild conditions with a high turnover frequency (TOF). Hence, this work provides a nitro-functionalized metal cluster-based nanoporous metal–organic framework with a wide range of potential applications such as catalysis, gas adsorption, and separation

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Antifungal activity of phenolic monoterpenes and structure-related compounds against plant pathogenic fungi

<p>The aim of this work is to explore the possibility of using the phenolic monoterpenes (PMs) as leading compounds with antifungal activity against plant disease. The <i>in vitro</i> antifungal activities of carvacrol and thymol against seven kinds of plant pathogenic fungi were evaluated on mycelium growth rate method, and the results showed that carvacrol and thymol exhibited broad spectrum antifungal activity. Structure requirement for the antifungal activity of PMs was also investigated. The preliminary conclusion was that phenolic hydroxyl and monoterpene were basic structures for the antifungal activity of PMs, and the position of phenolic hydroxyl showed less effect. Ester derivatives of carvacrol and thymol were more effective than carvacrol and thymol against plant pathogenic fungi. We suggested that carvacrol, thymol and their ester derivatives could potentially be used as new fungicide leading compounds.</p

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands

Ancillary Ligands Dependent Structural Diversity of A Series of Metal–Organic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

A series of novel multidimensional transition metal–organic frameworks (MOFs), [Cu­(Hbcpb)₂]_<i>n</i> (<b>1</b>), [Co­(bcpb)]_<i>n</i> (<b>2</b>), [Co­(Hbcpb)₂(1,4-bib)]<i>n</i> (<b>3</b>), {[M­(bcpb)­(1,4-bimb)]·xH₂O}<i>n</i> (<i>M</i> = Co (<b>4</b>), Cu (<b>5</b>), Ni (<b>6</b>), <i>x</i> = 1 for <b>5</b>, 2 for <b>4</b> and <b>6</b>), [Co­(bcpb)­(4,4′-bibp)]_<i>n</i> (7), {[Co­(bcpb)­(4,4′-bibp)]·2H₂O}_<i>n</i> (<b>8</b>), and [Ni₂(bcpb)₂(4,4′-bimbp)₂]_<i>n</i> (<b>9</b>), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis­(3-carboxyphenyl)­pyridine, 1,4-bib = 1,4-bis­(1H-imidazol-4-yl)­benzene, 1,4-bimb = 1,4-bis­(imidazol-1-ylmethyl)­benzene, 4,4′-bibp = 4,4′-bis­(imidazol-1-yl)­biphenyl, 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^– form in <b>1</b> and <b>3</b>, and completely deprotonated to afford the bcpb^2– form in <b>2</b> and <b>4</b>–<b>9</b>. Complex <b>1</b> exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schläfli symbol of (4³)₂(4⁶·6⁶·8³). The three-dimensional (3D) framework of <b>2</b> is defined as a (4,4)-connected pts topology with the Schläfli symbol of (4²·8⁴). Complex <b>3</b> displays a (4,6)-connected pcu topology with the Schläfli symbol of (4¹²·6³) built from 4⁴ 2D nets with the help of 1,4-bib. Complexes <b>4</b>–<b>6</b> are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schläfli symbol of (4·6²)­(4·6⁶·8³). The supramolecular isomers of <b>7</b> and <b>8</b>, resulted from the different pH in the reaction, exhibit (3,5)-connected (4²·6⁷·8)­(4²·6) 3,5-L2 and (4,6)-connected (4⁴·6¹⁰·8)­(4⁴·6²) fsc topology, respectively. Complex <b>9</b> can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schläfli symbol of (4²·6⁵·8³)­(4²·6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands