Deciphering supramolecular isomerization in coordination polymers: connected molecular squares vs. fused hexagons.

The self-assembly of Mn(ii), bis(tridentate) ligands and bent dicarboxylate linkers under ambient conditions has been exploited to generate a series of 1D coordination polymers in good yields. For a set of seven compounds, structural isomerization of these architectures is demonstrated through the variation of length and nature of the spacer between the tridentate capping sites of the bis(tridentate) ligands, such as tpbn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-1,4-diaminobutane), tphxn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-1,6-diaminohexane), and tpxn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-xylylamine) or by varying the bent dicarboxylate linker 4,4'-(dimethylsilanediyl)bis-benzoic acid (H2L1) or 4,4'-oxybis-benzoic acid (H2L2). These compounds have been structurally characterized by single-crystal and powder X-ray diffraction, FTIR, and thermogravimetric and elemental analyses. This study reveals that the supramolecular structural variation can be precisely controlled either by a judicious selection of reaction conditions or linker/ligand combinations. For example, the self-assembly of Mn(ii), tpbn and H2L1 in DMF/EtOH/water affords a mixture of products (1 and 1a) while changing the solvent combination to EtOH/water results in the generation of a single isomer (1a) in a highly selective manner. On the other hand, for the Mn(ii)-tphxn system, different structural isomers have been isolated by varying the dicarboxylates, H2L1 and H2L2 (2vs.5). Similarly, for the Mn(ii)-H2L2 system, a variation in the spacer chain length of bis(tridentate) ligands, tpbn and tphxn resulted in the formation of different structural isomers (4vs.5).

Effecting structural diversity in a series of Co(II)-organic frameworks by the interplay between rigidity of a dicarboxylate and flexibility of bis(tridentate) spanning ligands.

In a one-pot self-assembly reaction of Co(OAc)2·4H2O, thiophene-2,5-dicarboxylic acid (H2tdc) and four different bis(tridentate) polypyridyl spanning ligands under ambient conditions, a series of structurally diverse metal-organic frameworks has been synthesised and characterized by single crystal X-ray diffraction: {[Co2(tdc)2(tpbn)(H2O)2]·solvent}n (solvent = 2H2O, 1; solvent = 2CH3OH, 2H2O, 1a), {[Co2(tdc)2(tphn)]·solvent}n (solvent = H2O, 2; solvent = CH3OH, 2.5H2O, 2a), {[Co2(tdc)2(tpchn)(H2O)2]·solvent}n (solvent = 5H2O, 3; solvent = C2H5OH, 2H2O, 3a), and {[Co2(tdc)2(tpxn)]·solvent}n (solvent = 6H2O, 4; when no solvent, 4a), where tpbn (N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,4-diaminobutane), tphn = N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,6-diaminohexane, tpchn = N,N'-(cyclohexane-1,4-diylbis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) and tpxn = N,N'-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine). There is a profound effect of the nature of spacer between the alkyl nitrogens in the spanning ligands (flexible vs. semiflexible) on the molecular structures of 1a-4a. The notable differences are (a) the binding mode of the tridentate part of polypyridyl ligands to the Co(ii) center is facial in 1a, 3a and 4a but meridional in 2a, (b) the Co(ii) centers in 1a-3a are hexacoordinated (with a coordinated water in 1a and 3a) but are pentacoordinated in 4a, and (c) the binding mode of tdc linker is bis(monodentate) in 1a, 3a and 4a but chelated in one end and monodentate in the other end in 2a. Thus, the overall framework structure of 1a, 2a, 3a and 4a is cis-decalin type 2D polymer, ladder-shaped 1D polymer, hexagonal 2D net and cis-decalin type 2D polymer, respectively. Their thermal stabilities have been established by thermogravimetric analysis (TGA). The presence of an unsaturated metal center in 4 has provided us an opportunity for its use as an efficient Lewis acid catalyst for the Knoevenagel condensation reaction of malononitrile with various aldehydes (100% conversion in 60 minutes with 2 mol% catalyst in methanol).

Ruthenium Catalyzed C-H Acylmethylation of N-Arylphthalazine-1,4-diones with α-Carbonyl Sulfoxonium Ylides: Highway to Diversely Functionalized Phthalazino-fused Cinnolines.

A direct ortho-Csp2 -H acylmethylation of 2-aryl-2,3-dihydrophthalazine-1,4-diones with α-carbonyl sulfoxonium ylides is achieved through a RuII -catalyzed C-H bond activation process. The protocol featured high functional group tolerance on the two substrates, including aryl-, heteroaryl-, and alkyl-substituted α-carbonyl sulfoxonium ylides. Thereafter, 2-(ortho-acylmethylaryl)-2,3-dihydrophthalazine-1,4-diones were used as potential starting materials for the expeditious synthesis of 6-arylphthalazino[2,3-a]cinnoline-8,13-diones and 5-acyl-5,6-dihydrophthalazino[2,3-a]cinnoline-8,13-diones under Lawesson's reagent and BF3 ⋅OEt2 mediated conditions, respectively. Of these, the BF3 ⋅OEt2 -mediated cyclization proceeded in DMSO as a solvent and a methylene source via dual C-C and C-N bond formations.