A tetrahedral FeII4L4 cage assembled from the coordination of triangular chiral, face-capping ligands to iron(II). This exists as two diastereomers in solution, which differ stereochemistry their metal vertices, but share same point chirality ligand. The equilibrium between these was subtly perturbed by guest binding. perturbation correlated with size and shape fit within host; insight interplay provided atomistic well-tempered metadynamics simulations. understanding thus gained...

The discovery of new compounds with pharmacological properties is usually a lengthy, laborious and expensive process. Thus, there increasing interest in developing workflows that allow for the rapid synthesis evaluation libraries aim identifying leads further drug development. Herein, we apply combinatorial to build library 90 iridium(III) complexes (81 which are new) over two synthesise-and-test cycles, potential agents photodynamic therapy. We demonstrate power this approach by highly...

An adj-dicarbacorrole with CCNN in the core is achieved by replacing bipyrrole moiety a simple polycyclic aromatic hydrocarbon, such as biphenyl unit. Spectroscopic studies and structural analyzes confirm absence of macrocyclic aromatization, thus leading to overall nonaromatic character. The trianionic effectively utilized stabilize copper(III) ion form an organocopper complex.

In the corrole homologue, 6,11,16-triarylbipyricorrole, bipyrrole unit is replaced by a 2,2'-bipyridine unit. This modification effectively alters N4 coordination sphere from trianionic [(NH)3 N] to monoanionic [N3NH] state. The newly formed core stabilizes Zn(II) ions with enhanced emission properties. was further utilized for metal ion sensing studies and exploited selective detection of ions.

Ion channels are ubiquitous in Nature, performing complex and essential tasks our bodies. Synthetic chemists have begun to understand how form artificial channels, which hold great promise as components cells, synthetic biology more widely. Future generations of these systems will be critical the treatment channelopathies; diseases where ion malfunction, challenging treat with current modalities. Despite advances design transporters, generation cannot approach selectivity controllability...

Abstract An unstable conjugated homoporphyrin was successfully stabilized by introducing meso ‐aryl substitutents. It evident from the moderate diatropic ring current found NMR analysis that newly formed 20π free base and its protonated form exhibited Möbius aromatic character. Furthermore, complexation as a ligand with an Rh I ion afforded unique binding mode retained aromaticity. Overall, these compounds are smallest molecules, confirmed spectral crystal‐structure supported theoretical studies.

Abstract An adj ‐dicarbacorrole with CCNN in the core is achieved by replacing bipyrrole moiety a simple polycyclic aromatic hydrocarbon, such as biphenyl unit. Spectroscopic studies and structural analyzes confirm absence of macrocyclic aromatization, thus leading to overall nonaromatic character. The trianionic effectively utilized stabilize copper(III) ion form an organocopper complex.

The Pd(II) complex of 5,15-porphodimethene is shown as a chemodosimetric sensor where it selectively senses cyanide ions, monitored through electronic spectral analysis and identified by the naked eye. possible binding mechanism also proposed based on (1)H NMR analyses. Two polymorphs mentioned are obtained using different polar solvents further confirmed single crystal X-ray

Stable homocarbaporphyrinoids were successfully synthesized by incorporating the m-o-m and p-o-p terphenyl units into porphyrin core. The distinct bonding modes of in macrocycle generated two structural isomers with four carbon atoms macrocyclic environment. core was utilized to stabilize RhI ion. spectral analyses revealed that restricted (m-o-m) allowed (p-o-p) conjugation provide overall non-aromatic characteristics both free bases their complexes.

(Porphyrinyl)dicyanomethyl radicals were produced by oxidation of dicyanomethyl-substituted porphyrins with PbO₂.

Abstract Stable B III ‐subporphyrin‐substituted dicyanomethyl radicals were synthesized by S N Ar reaction of meso ‐bromo‐ or ‐chlorosubporphyrins with malononitrile followed oxidation PbO 2 . Different from previously reported that underwent σ‐ π‐dimer formation both in the solid state and solutions, subporphyrin‐stabilized exist as monomers solutions even at low temperature. DFT calculations revealed efficient spin delocalization over entire subporphyrin. In state, these form weak π‐dimers...

Carbatriphyrin(3.1.1) is the structural isomer of biphenylcorrole and achieved by switching bonding mode biphenyl unit from 3,3' to 2,3' which turns corrole into a triphyrin analogue. The presence m-arene in framework restricts overall conjugation thus leads nonaromatic macrocycle. protonation experiments afford trifluoroacetate ion complex. coordination chemistry reveals that bottom approach boron(III) forms weak C-H⋅⋅⋅B interactions, however top stabilizes organoborane complex product...

A new rectangular-shaped carbadecaphyrin was successfully synthesized by introducing a terphenylene unit (m-m-m) in the macrocyclic core. The moiety offers an open framework with multiple binding pockets to stabilize two Rh(I) ions photophysical and structural studies reveal non-aromatic character of ligand its bis-Rh(I) complex.

Abstract In the corrole homologue, 6,11,16‐triarylbipyricorrole, bipyrrole unit is replaced by a 2,2′‐bipyridine unit. This modification effectively alters N4 coordination sphere from trianionic [(NH) 3 N] to monoanionic [N NH] state. The newly formed core stabilizes Zn II ions with enhanced emission properties. was further utilized for metal ion sensing studies and exploited selective detection of ions.

2,18-Bis(dicyanomethyl)-substituted NiII porphyrin 8 and ZnII 11 were prepared subjected to oxidation with PbO2 in CH2 Cl2 at 298 K give cyclophane-type chlorin dimers (9)2 (12)2 as a consequence of double recombination biradicals 9 12, respectively. Dimer takes syn-conformation two distorted chlorins but an anti-conformation relatively planar chlorins. At K, dimer is stable its 1 H NMR spectrum sharp becomes broad high temperature, while the considerably even sharper low temperature. These...

Isosmaragdyrin with an N3C2 core is successfully achieved by introducing a 2,6-di-m-phenylpyridine unit. The utilized to stabilize the Rh(i) ion in N-Rh(i)-N bonding mode and Pt(ii) (N^C)N fashion form unsymmetrical pincer-type organometallic complex.

Three distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis-4,4'-biphenyl units in the macrocyclic core. The free-base form adopts a figure-eight conformation, whereas protonation triggers change with pyrrole ring inversion and acquires an open-framework structure. insertion bis-RhI metal ion core affords singly twisted Furthermore, local aromaticity dominates overall all three forms, thus nonaromatic characteristics. These results are supported spectral...

While oxidation of 5,5',15,15'-tetramesityl-10-10'-linked 3NH-corrole dimer with DDQ gave the corresponding triply linked 2NH-corrole tape, use an equimolar amount p-chloranil as a milder oxidant resulted in formation 10-10'-linked neutral radical stable product. The stability this peculiar product is ascribed largely to strong antiferromagnetic interaction two spins. Further diradical produced corrole suggesting its involvement reaction intermediate tape. Oxidation bis-pyridine-coordinated...

A series of donor–acceptor compounds based on a sub-porphyrin (SubP) as an electron donor and naphthyldiimide (NDI) acceptor has been designed, synthesized investigated by time-resolved emission transient absorption measurements.

Abstract The discovery of new compounds with pharmacological properties is usually a lengthy, laborious and expensive process. Thus, there increasing interest in developing workflows that allow for the rapid synthesis evaluation libraries aim identifying leads further drug development. Herein, we apply combinatorial to build library 90 iridium(III) complexes (81 which are new) over two synthesise‐and‐test cycles, potential agents photodynamic therapy. We demonstrate power this approach by...

An o-p-biphenyl moiety-incorporated 32π hexaphyrin(3.1.1.3.1.1) is successfully achieved. Replacing ortho with meta connectivity in the biphenyl unit of hexaphyrin leads to formation its structural isomer, octaphyrin(1.1.1.0.1.1.1.0). Spectral and analyses reveal lack planarity presence an m-arene octaphyrin, thus affording nonaromatic characteristics.

The discovery of new compounds with pharmacological properties is usually a lengthy, laborious and expensive process. Thus, there increasing interest in developing workflows that allow for the rapid synthesis evaluation libraries aim identifying leads further drug development. Herein we report on such workflow over 80 iridium(III) complexes as phototoxic agents against cancer cells. We demonstrate it possible to complete whole semiautomated within 72 hours, allowing library iteration. This...

Abstract An unstable conjugated homoporphyrin was successfully stabilized by introducing meso ‐aryl substitutents. It evident from the moderate diatropic ring current found NMR analysis that newly formed 20π free base and its protonated form exhibited Möbius aromatic character. Furthermore, complexation as a ligand with an Rh I ion afforded unique binding mode retained aromaticity. Overall, these compounds are smallest molecules, confirmed spectral crystal‐structure supported theoretical studies.

Abstract 2,18‐Bis(dicyanomethyl)‐substituted Ni II porphyrin 8 and Zn 11 were prepared subjected to oxidation with PbO 2 in CH Cl at 298 K give cyclophane‐type chlorin dimers ( 9 ) 12 as a consequence of double recombination biradicals , respectively. Dimer takes syn ‐conformation two distorted chlorins but an anti relatively planar chlorins. At K, dimer is stable its 1 H NMR spectrum sharp becomes broad high temperature, while the considerably even sharper low temperature. These results...