title: Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces.
abstract: Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP.
authors: School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou, Jiangsu 221116, People's Republic of China; andDepartment of Chemistry, University of Utah, Salt Lake City, UT 84112 stang@chem.utah.edu yhshi@jsnu.edu.cn.
authors: Yanhui
authors: Y
authors: Shi
authors: Department of Chemistry, University of Utah, Salt Lake City, UT 84112.
authors: Irene
authors: I
authors: Sánchez-Molina
authors: School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou, Jiangsu 221116, People's Republic of China; and.
authors: Changsheng
authors: C
authors: Cao
authors: Department of Chemistry, University of Utah, Salt Lake City, UT 84112.
authors: Timothy R
authors: TR
authors: Cook
authors: Department of Chemistry, University of Utah, Salt Lake City, UT 84112 stang@chem.utah.edu yhshi@jsnu.edu.cn.
authors: Peter J
authors: PJ
authors: Stang
mesh_terms: D032701:Biomimetics / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D015394:Molecular Structure; D046912:Multiprotein Complexes / Q000096:biosynthesis* / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*; D015202:Protein Engineering / Q000379:methods*; D013816:Thermodynamics; D015032:Zinc / Q000737:chemistry
chemical_list: D046912:Multiprotein Complexes; D011166:Porphyrins; D010984:Platinum; D015032:Zinc
keywords: metallacages; supramolecular chemistry