Crystal structure of a μ3-oxo-hexakis-(μ2-carboxylatopyridine-O,O)-triaquatrichromium(III) perchlorate, {[Cr3O(i-C6H5O2N)6(H2O)3]-(ClO4)7·3NaClO4·3H2O}

The asc Trinodal Platform: Two‐Step Assembly of Triangular, Tetrahedral, and Trigonal‐Prismatic Molecular Building Blocks

“…Uninodal nets with one kind of vertex are well represented and include those sustained by 3-(srs, [3] ths [4] ), 4-(dia, [5] nbo [6] ), 6-(pcu, [1d, 4b, 7] acs [8] ), 8-(bcu [9] ), or 12-(fcu [10] ) connected nodes. [19] The hexapyridyl variant, tp-PMBB-1, is soluble, cheap, and robust and can subsequently be used for the preparation of binodal nets. [11] High-symmetry MBBs have also been exploited to generate binodal nets with one kind of edge (edge-transitive) [12] in which the second node is a 3-connected organic moiety, as exemplified by the following nodes: copper-paddlewheel [Cu 2 (CO 2 ) 4 ] (3,4-c, tbo, [13] pto [14] ) square MBBs; basic zinc acetate [Zn 4 (m 4 -O)-(CO 2 ) 6 ] octahedral MBBs (6,3-c, qom).…”

“…We address these handicaps herein by applying our recently reported two-step crystal engineering strategy [18] to generate the first trinodal MOM platform.The two-step approach relies upon first preparing a trigonal-prismatic primary molecular building block (tp-PMBB) based on [Cr 3 (m 3 -O)(CO 2 ) 6 ] clusters decorated with six coordinating ligands (Figure 1). [19] The hexapyridyl variant, tp-PMBB-1, is soluble, cheap, and robust and can subsequently be used for the preparation of binodal nets. [18] Herein, we describe how tp-PMBB-1 can be reacted with tetrahedral (Zn 2+ , Cd 2+ ) and three triangular MBBs (1,3,5-benzenetricarboxylic acid, H 3 btc; 1,3,5-tris(4-carboxyphenyl) benzene, H 3 btb; 4,4',4''-[1,3,5-benzenetriyltris(carbonylimino)] trisbenzoic acid, H 3 btctb) in N,N-dimethylformamide (DMF; see the Supporting Information for further details) to afford the first four examples of trinodal networks involving triangular, tetrahedral, and trigonal-prismatic building blocks.The prototypal compound, tp-PMBB-1-asc-1, is based upon trigonal-prismatic clusters [Cr 3 O(isonic) 6 (H 2 O) 3 ] + (isonic = pyridine-4-carboxylate) coordinated to six tetrahedral Zn 2+ cations that are in turn coordinated to two triangular btc 3À anions.…”

“…The two-step approach relies upon first preparing a trigonal-prismatic primary molecular building block (tp-PMBB) based on [Cr 3 (m 3 -O)(CO 2 ) 6 ] clusters decorated with six coordinating ligands ( Figure 1). [19] The hexapyridyl variant, tp-PMBB-1, is soluble, cheap, and robust and can subsequently be used for the preparation of binodal nets. [18] Herein, we describe how tp-PMBB-1 can be reacted with tetrahedral (Zn 2+ , Cd 2+ ) and three triangular MBBs (1,3,5-benzenetricarboxylic acid, H 3 btc; 1,3,5-tris(4-carboxyphenyl) benzene, H 3 btb; 4,4',4''-[1,3,5-benzenetriyltris(carbonylimino)] trisbenzoic acid, H 3 btctb) in N,N-dimethylformamide (DMF; see the Supporting Information for further details) to afford the first four examples of trinodal networks involving triangular, tetrahedral, and trigonal-prismatic building blocks.…”

Network Diversity through Decoration of Trigonal‐Prismatic Nodes: Two‐Step Crystal Engineering of Cationic Metal–Organic Materials

“…[9] Such linkers complement synthetically accessible and highly symmetrical metal carboxylate nodes such as [Cu 2 (CO 2 ) 4 ], [Zn 4 (m 4 -O)-(CO 2 ) 6 ] and [{M 3 (m 3 -O)(CO 2 )} 6 ] (M = Cr, Fe). The first three examples of such nets, tp-PMBB-1snx-1, -snw-1, and -stp-1 (nomenclature describes both the primary building block and the topology of the resulting net) are described herein.The building block tp-PMBB-1 [Cr 3 (m 3 -O)(isonic) 6 ] + (isonic = pyridine-4-carboxylate) [16] represents a discrete and robust "hexapyridyl" 6-connected node that is well-suited for the subsequent synthesis of a plethora of networks with nanoscale features. [{M 3 (m 3 -O)(CO 2 )} 6 ], the "trigonal prism", has also afforded highly porous materials, as exemplified by MIL-100 [12] and MIL-101.…”

“…The building block tp-PMBB-1 [Cr 3 (m 3 -O)(isonic) 6 ] + (isonic = pyridine-4-carboxylate) [16] represents a discrete and robust "hexapyridyl" 6-connected node that is well-suited for the subsequent synthesis of a plethora of networks with nanoscale features. Its coordination chemistry with two metals is detailed herein: a linear but bendable linker (Ag + ) and a rigid square-planar metal node (Cd 2+ ).…”