ABSTRACT
A thermoresponsive, 3D hinged metal-organic framework (HMOF-1) assembled from meso-tetra(4-pyridyl)porphine and CdI(2) exhibits a 3D "lattice fence" topology with extraordinary thermal expansion and shrinkage. A simple structural model is established to elucidate such a drastic thermal response. The hinged structure model presented here can also be applied to other "lattice fence" topologies with little or no modification, depending on the symmetry of the molecular building blocks.
ABSTRACT
We demonstrate how a single-crystal to single-crystal transformation resulting from bridging-linker replacement is possible in extended 2D and 3D metal-organic frameworks (MOFs) by introducing pillared paddlewheel MOF structures into a solution containing dipyridyl linkers. No lateral movement of the layers was observed during this transformation, creating a templating effect from the "parent" structure to the "daughter" structure. A previously unattainable structure was obtained by a two-step synthetic method utilizing the bridging-linker replacement transformation method. Additionally, a bridging-linker insertion was observed when excess linker was used with the 2D MOF structure, inducing an overall 2D to 3D transformation.
ABSTRACT
We demonstrate how a bioinspired synthetic approach can help organic linkers distinguish between different types of metal centers in metal-organic frameworks (MOFs). Modification of an organic building unit with methyl groups enables the unit to selectively coordinate to one of the two metal sites present in the MOFs. We report four new porphyrin-based, pillared-paddlewheel frameworks: PPF-11-Zn/Zn, -Co/Co, -Mn/Zn, and -Fe/Zn, where the first and second metals indicate the metal center for the porphyrin core and paddlewheel cluster, respectively. These compounds exhibit 3D MOFs in which 2D layers are pillared by a sterically controlled bipyridine, leaving the metal centers inside the porphyrin structurally unconnected.
Subject(s)
Organometallic Compounds/chemistry , 2,2'-Dipyridyl/chemistry , Enkephalin, Leucine/analogs & derivatives , Enkephalin, Leucine/chemistry , Models, Molecular , Zinc/chemistryABSTRACT
We report three new porphyrin-based, pillared paddle-wheel homologous series: porphyrin paddle-wheel frameworks PPF-3, -4, and -5. These compounds are assembled from free base or palladium tetrakis(4-carboxyphenyl)porphine, M(NO(3))(2) (M = Co and Zn), and 4,4'-bipyridine via solvothermal reactions. The resulting solids exhibit 3D metal-organic frameworks, where 2D layers are pillared by bipyridine with three different packing arrangements.
ABSTRACT
The electronic absorption spectra, photobleaching property, emission, and triplet excited state characteristics of a pentaazadentate porphyrin-like gadolinium(III) complex have been investigated at acidic and basic conditions. The electronic absorption spectrum of this complex exhibits a Soret band at ca. 449 nm and a Q-like band at ca. 880 nm when the pH value of the solution is lower than 6.6. At basic conditions, the Q-like band blue shifts to ca. 624 nm, while the Soret band only shows an approximate 20 nm hyposochromic shift. The acidic solution is relatively stable upon exposure to ambient light, but the basic solution photobleached to colorless in approximately 3 hours. Irradiation of the Soret band of basic solutions at 420 nm causes faster photobleaching than irradiation of the Q-like band (624 nm). The emission of this complex at pH = 6.5 appears at ca. 915 nm (max.) and 1016 nm, which is a mirror image of the Q-like band, indicating the nature of the emitting state being the lowest singlet excited state. At pH = 9.0, the emission band shifts to ca. 585 nm (max.) and 630 nm (shoulder). The triplet transient difference absorption spectrum of the solution at pH = 6.5 exhibits a bleaching band at ca. 460 nm, a narrow positive band at ca. 450 nm, and a broad, moderately intense absorption band from 480 nm extending to the near-IR region (700 nm). The triplet excited state lifetime deduced from the decay of the transient absorption is approximately 81 ns.
