Unravelling the Growth of Supramolecular Metal–Organic Frameworks Based on Metal-Nucleobase Entities
2015; American Chemical Society; Volume: 15; Issue: 2 Linguagem: Inglês
10.1021/cg501804h
ISSN1528-7505
AutoresJintha Thomas‐Gipson, Rubén Pérez‐Aguirre, Garikoitz Beobide, Óscar Castillo, Antonio Luque, Sonia Pérez‐Yáñez, P. Román,
Tópico(s)Crystallography and molecular interactions
ResumoThe present work provides the basis to obtain three-dimensional (3D) extended porous supramolecular assemblies named supramolecular metal–organic frameworks (SMOFs). This goal can be achieved by considering three key factors: (i) the use of rigid building units, (ii) the establishment of predictable and rigid synthons between the building units, and (iii) the non-coplanarity of functional groups involved in the predictable synthons. Throughout this report we demonstrate the suitability of this synthetic strategy supported by six new SMOFs based on metal-nucleobase entities which fulfill the stated requirements: [Co(ThioG)3] (SMOF-4; ThioG = thioguaninato), [Co(Hade)2X2] (SMOF-5, SMOF-6; Hade = adenine and X = Cl–, Br–), [Cu8(μ3-OH)4(μ4-OH)4(ade)4(μ-ade)4(μ-Hade)2] (SMOF-7; ade = adeninato), [Cu4(μ3-ade)4(μ-ade)2(pentylNH2)2(CH3OH)2(CO3)2(H2O)2] (SMOF-8; pentylNH2 = 1-pentylamine), and [Cu2(μ-ade)2(ade)(μ-OH)(H2O)(CH3OH)]n (SMOF-9). SMOF-4 is built up from monomeric entities in which bidentate thioguaninato ligands establish complementary hydrogen bonding interactions in non-coplanar directions leading to supramolecular layers that are further connected resulting in a porous structure with one-dimensional (1D) channels. The hydrogen bonding interactions among Watson–Crick and sugar edges of monomeric entities in SMOF-5 give rise to a triply interpenetrated supramolecular framework. Octameric clusters in SMOF-7 are self-assembled by hydrogen bonding to yield a porous 3D network. SMOF-8 is built up from tetranuclear units that are linked via base pairing interactions involving Watson–Crick faces to afford layers whose assembly generates a two-dimensional pore system. SMOF-9 is in between pure MOFs and SMOFs since it consists of 1D infinite coordination polymers held together by complementary hydrogen bonding interactions into a 3D supramolecular porous structure.
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