A molecular cage {Au (μ-PAnP) [Fe(H O) (TPyP)] (OTf) }(OTf) (1) composed of two cofacial Fe -porphyrin can be self-assembled from the gold clip [Au (PAnP)Cl ] and Fe (H O) (TPyP) (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au (μ-PAnP) [Fe (μ-O)(TPyP) ]}(OTf) (2), which has a height of ≈4.4 Å and porphyrin-porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe (μ-O)(TPyP) . The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh ) [Fe (μ-O)(TPyP) ]}(OTf) (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.201803501 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Multitopic Corannulene-Porphyrin Hosts for Fullerenes: A Three-Layer Scaffold for Precisely Designed Supramolecular Ensembles.
Org Lett
January 2025
GIR MIOMeT, IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Valladolid E47011, Spain.
A method to synthesize cofacial dimeric porphyrins bearing eight corannulene units has been developed. It relies on the stability of octahedral CO-capped Ru(II) complexes linked by N-donor ligands. This specific arrangement provides an optimal scaffold to accommodate fullerenes by imposing corannulene groups at a precise distance and relative orientation.
View Article and Find Full Text PDFOptically active cofacial ABCD-Pt(II)-porphyrin dimer exhibits bright circularly polarized phosphorescence.
Chem Commun (Camb)
January 2025
Department of Applied Chemistry for Environment, School of Biological and Environmental Sciences, Kwansei Gakuin University 1 Gakuen Uegahara, Sanda, Hyogo 669-1330, Japan.
Article Synopsis
- The synthesis of a chiral cofacial ABCD-Pt(II)-porphyrin dimer was successfully completed using a Pt-templated method followed by a Suzuki-Miyaura cross-coupling process.
- The resulting enantiomers showcased bright red circularly polarized phosphorescence.
- The phosphorescence had a high value of over 10 M cm, indicating strong optical properties.
Gram-Scale, One-Pot Synthesis of a Cofacial Porphyrin Bridged by Ortho-xylene as a Scaffold for Dinuclear Architectures.
Inorg Chem
November 2024
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York14260, United States.
Herein, we report the reaction between four 1,2-dibromoxylenes and two tetra-3-pyridylporphyrins for the formation of a cofacial porphyrin core spanned by dipyridinium xylene moieties. The metal-free organic nanocage (oNC) was synthesized in one twenty-four h step at a gram-scale with a 91.5% yield.
View Article and Find Full Text PDFPorous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.
Angew Chem Int Ed Engl
November 2024
EaStChem, School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh, EH9 3FJ, UK.
Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2',6'-di-iso-propylphenoxy)phthalocyanine or some of its metal complexes [(dipPhO)PcM; M=H, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)PcM, which is driven by the complementary shape and symmetry of the two macrocycles.
View Article and Find Full Text PDFRare Guest-Induced Electrical Conductivity of Zn-Porphyrin Metallacage Inclusion Complexes Featuring π-Donor/Acceptor/Donor Stacks.
ACS Appl Mater Interfaces
January 2024
Department of Chemistry, Clemson University, 211 S. Palmetto Blvd., Clemson, South Carolina 29634, United States.
Charge-transfer (CT) interactions between co-facially aligned π-donor/acceptor (π-D/A) arrays engender unique optical and electronic properties that could benefit (supra)molecular electronics and energy technologies. Herein, we demonstrate that a tetragonal prismatic metal-organic cage (MOC1) having two parallel π-donor tetrakis(4-carboxyphenyl)-Zn-porphyrin (ZnTCPP) faces selectively intercalate planar π-acceptor guests, such as hexaazatriphenylene hexacarbonitrile (HATHCN), hexacyanotriphenylene (HCTP), and napthanelediimide (NDI) derivatives, forming 1:1 πA@MOC1 inclusion complexes featuring supramolecular π-D/A/D triads. The π-acidity of intercalated π-acceptors (HATHCN ≫ HCTP ≈ NDIs) dictated the nature and strength of their interactions with the ZnTCPP faces, which in turn influenced the binding affinities () and optical and electronic properties of corresponding πA@MOC1 inclusion complexes.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!