Search

Metal–organic frameworks with tunable functional groups like solid-solution have received considerable interest. In this paper, a crs-type structure built of [Zn3(OH)(dmtrz)3] triazolate-trinuclear and [Zn2(COO)4] paddlewheel units, linked by 3,5-dimethyl-1,2,4-triazolate (dmtrz) and isophthalate (ipa) ligands (named as MAC-4-A), has been used as a prototype framework. Four types of functional groups (B: 5-hydroxyisophthalate, C: 5-aminoisophthalate, D: 5-ethoxyisophthalate, and E: 5-acetamidoisophthalate) have been integrated into the framework, giving isostructures of MAC-4-B to E, respectively. Then, by the solid-solution framework approach, four group samples are prepared, which are MAC-4-AB-x, MAC-4-AC-x, MAC-4-AD-x, and MAC-4-AE-x (x denoted as the ratio of functional ligands in the framework, x = 0.3, 0.5, 0.7), and their CO2 and N2 adsorptions have been studied. Our results revealed that the CO2 capacity is enhanced with the increase of functional groups and then decreases, showing a maximum uptak...

Two metal–organic frameworks containing a geometrically spin-frustrated trinuclear-triangular copper cluster ([Cu3O]) have been successfully isolated, which are {[Cu4.5(μ3-OH)(dmtrz)3(m-bdc)2.5(H2O)2(CH3OH)(DMF)]·DMF·5H2O}n (MAC-8) and {[Cu5(μ3-OH)(dmtrz)3(bdc)3(H2O)4]·3H2O}n (MAC-9) (Hdmtrz = 3,5-dimethyl-1H-1,2,4-triazole, H2m-bdc = 1,3-benzenedicarboxylic acid, H2bdc = 1,4-benzenedicarboxylic acid, DMF = N′,N-dimethylformamide). Magnetic and gas adsorption studies revealed the successful combination of strong antiferromagnetic properties (Jav = −106.6 and −113.7 cm–1 for [Cu3O] in MAC-8 and MAC-9, respectively) and high surface areas (1058 m2/g for MAC-8 and 1242 m2/g for MAC-9) in both of the structures. Further structural studies revealed that the high surface areas could be ascribed to the unique two-dimensional hexagonal pattern of [Cu3(O)] clusters, in which the [Cu3(O)] clusters are connected to each other in an end-end fashion via mononuclear copper ions/paddle-wheel units.

Seven new metal–organic frameworks (MOFs) have been synthesized using different organic amines as templates: [Cd(HBTC)2]·2(HDETA)·4(H2O) (1) (BTC = 1,3,5-benzenetricarboxylate and DETA = diethylenetriamine), [Cd2(BTC)2(H2O)2]·2(HCHA)·2(EtOH)·2(H2O) (CHA = cyclohexylamine) (2), [Cd5(BTC)4Cl4]·4(HTEA)·2(H3O) (TEA = triethylamine) (3), [Cd3(BTC)3(H2O)]·(HTEA)·2(H3O) (4), [Zn(BTC)(H2O)]·(HTPA)·(H2O) (TPA = tri-n-propylamine) (5), [Cd(BTC)]·(HTPA)·(H2O) (6), and [Cd2(BTC)(HBTC)]·(HTBA)·(H2O) (TBA = tri-n-butylamine) (7). Topologically, the polymer 1 exhibits a two-dimensional (2D) Cd-HBTC network with (44) topology, which is a sql structure; the polymer 2 possesses a three-dimensional (3D) porous Cd-BTC framework with (4·62)2(42·610·83) topology, which is a contorted rutile structure; polymer 3 exhibits a 3D open Cd-BTC architecture with (62·82·102)2(62·84)(63)4 topology; polymer 4 is a 3D porous Cd-BTC network with new (4·62)2(42·64·86·103)(6·82)2(62·84)(62·84)2(62·8)2 topology; similar to 1, polymer 5 is a 2...