•Two-interpenetrated microporous compounds.•Different stability.•Storage and separation of gases.Solvothermal synthesis afford two new porous metal-organic frameworks (MOFs): {[Cu6(L)3(H2O)4(py)2]·6(DMF)13(H2O)}n (1) and {[Cu6(L)3(H2O)6]·29(H2O}n (2). [5,5′-(1,3-phenylenebis(methylene))bis(oxy)diisophthalic acid (HL)]. Although possessing similar structures, the two MOFs have markedly different stabilities. Compound 1 and 2 can take up 16.8 mg/g and 15.9 mg/g of H2 at 77 K at 1 bar and 133 cm3/g and 120 cm3/g of H2 at 87 K (Fig. 8), which is higher than the performance of well-known MOFs PCN-6 and HKUST-1 at 77 K and 1 bar. Notably, both MOFs exhibited highly efficient, selective adsorption of CO2 over CH4 under ambient conditions. Such compounds may therefore prove useful for gas separation and purification.

•A 3D network based on the trinuclear cobalt(II) clusters is synthesized and characterized.•Topological analysis indicates that it has tfz-d network with the Schläfli symbol of (43)2(46·618·84).•The magnetic data reveals the dominant antiferromagnetic interactions between the Co (II) cations.A 3D network based on the trinuclear cobalt(II) clusters, [Co3(bta)2(bib)2] (1) (H3bta = 1,3,5-benzenetriacetic acid; bib = 1,3-bis(1-imidazoly)benzene), is synthesized and characterized. Topological analysis indicates that it has a unique binodal (3,8)-connected tfz-d network with the Schläfli symbol of (43)2(46·618·84). Interestingly, the magnetic data reveals the dominant antiferromagnetic interactions between the Co (II) cations within the trinuclear cluster.A 3D network based on the trinuclear cobalt(II) clusters, [Co3(bta)2(bib)2] (1) (H3bta = 1,3,5-benzenetriacetic acid; bib = 1,3-bis(1-imidazoly)benzene) have been synthesized and characterized. Topological analysis indicates that it has a unique binodal (3, 8)-connected tfz-d network with the Schläfli symbol of (43)2(46·618·84). The magnetic data reveals the dominant antiferromagnetic interactions between the Co (II) cations within the trinuclear cluster.

•A pcu network based on dinuclear Ni(II) units has been hydrothermally synthesized.•Two Ni(II) ions are bridged by two carboxylate groups in the syn-anti mode.•The dominant ferromagnetic interactions exist between Ni(II) ions.A pcu network based on the dinuclear Ni(II) units, [Ni2(hfipbb)2(1,3-bix)2]n (1) (H2hfipbb = 4,4′- (Hexafluoroisopropylidene)bis(benzoic Acid); 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene), has been hydrothermally synthesized and structurally characterized. Interestingly, the two Ni(II) cations are bridged by two carboxylate groups in the rarely-seen syn-anti mode. The magnetic data reveal the dominant ferromagnetic interactions between Ni(II) ions.Graphical abstractA pcu network based on the dinuclear Ni(II) units has been hydrothermally synthesized and structurally characterized. Interestingly, the two Ni(II) cations are bridged by two carboxylate groups in the rarely-seen syn-anti mode. The magnetic data reveals the dominant ferromagnetic interactions between the Ni(II) ions.

•A 3D ten-connected self-penetrating network is formed•The pentacobalt(II) clusters act as SBU•Ile-364345362 network is indicated•Antiferromagnetic interactions between the Co(II) cations are revealedA 3D ten-connected self-penetrating network based on the pentacobalt(II) clusters, [Co5(1,4-ndc)4(OH)2(1,3-bix)2]n (1) (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid; 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene), is synthesized and characterized. Topological analysis indicates that it has ile-364345362 network. The magnetic data reveals the dominant antiferromagnetic interactions between the Co(II) cations.A 3D ten-connected self-penetrating network based on the pentacobalt(II) clusters is synthesized and characterized, Topological analysis indicates that it has ile-364345362 network. The magnetic data reveals the dominant antiferromagnetic interactions between the Co(II) cations.