The title compound, tetraethylammonium dodeca-mu-cyano-hexacyanotetrakis(ethylenediamine)tetracadmium(II)triferrate(III), (C(8)H(20)N)[Cd(4)Fe(3)(CN)(18)(C(2)H(8)N(2))(4)], was prepared from a reaction mixture containing CdCl(2), K(3)[Fe(CN)(6)], ethylenediamine (en) and [Et(4)N]Br in a 1:1:3:1 molar ratio. The crystal structure consists of a negatively charged three-dimensional framework of [[Cd(en)](4)[Fe(CN)(6)](3]n)(n-) anions, with [Et(4)N](+) cations located in the cavities of the framework. The Cd atom is octahedrally coordinated by one disordered chelating en molecule [mean Cd-N = 2.35 (3) A] and four N-bonded bridging cyano groups [Cd-N distances are in the range 2.283 (2)-2.441 (2) A]. There are two crystallographically independent [Fe(CN)(6)](3-) anions in the structure and in each the Fe atom lies on a twofold axis. In the first [mean Fe-C = 1.941 (5) A], all the cyano groups are bridging ligands, while in the second [mean Fe-C = 1.945 (2) A], there are two terminal cyano ligands in trans positions. The Cd-N-C angles range from 128.6 (2) to 172.8 (2) degrees.
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http://dx.doi.org/10.1107/s0108270103010497 | DOI Listing |
J Biol Chem
January 2025
Department of Chemistry, The University of Texas at San Antonio, Texas 78249, United States. Electronic address:
MarE, a heme-dependent enzyme, catalyzes a unique 2-oxindole-forming monooxygenation reaction from tryptophan metabolites. To elucidate its enzyme-substrate interaction mode, we present the first X-ray crystal structures of MarE in complex with its prime substrate, (2S,3S)-β-methyl-L-tryptophan and cyanide at 1.89 Å resolution as well as a truncated yet catalytically active version in complex with the substrate at 2.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
Hindered tetraphenylethylene (hTPE) helicates are resolved into two left-handed (M) and right-handed (P) isomers by linkage and removal of chiral auxiliary (1,2,5)-menthol, furnishing gram-scale hTPE enantiomers via flash silica column chromatography. hTPE helicate enantiomers bearing electron-accepting cyano and electron-donating triphenylamine groups can emit deep-blue CPL signals with a fluorescence quantum yield surpassing 50%. Full-color and white-light emission were achieved by blending them with dyes in a poly(methyl methacrylate) (PMMA) film.
View Article and Find Full Text PDFOrg Lett
January 2025
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610068, People's Republic of China.
A novel Ru-catalyzed radical-triggered trifunctionalization of hexenenitriles is presented, employing a strategy of remote cyano group migration and -C(sp)-H functionalization. Through remote cyano migration, the alkenyl moiety undergoes difunctionalization to the formation of a benzylic radical intermediate. This intermediate facilitates -selective C-H bond addition relative to the C-Ru bond within the Ru(III) complex, ultimately enabling trifunctionalization.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450052, China.
We present a visible-light-promoted radical cascade cyclization reaction sulfonylmethylation, cyano insertion, and radical cyclization of unactivated alkenes bearing cyano groups. This strategy enables the rapid synthesis of sulfonylmethylated phenanthridines under mild conditions with broad substrate compatibility, operational simplicity, and mild reaction conditions. The developed approach provides a novel pathway for assembling complex polycyclic nitrogen-containing frameworks, addressing a critical synthetic challenge and expanding the toolbox of photochemical transformations in organic synthesis.
View Article and Find Full Text PDFChemistry
January 2025
The Hong Kong Polytechnic University, Department of Applied Biology and Chemical Technology, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Hom, Hong Kong (P.R. China), 000000, Hong Kong, HONG KONG.
A series of new (donor)₂-donor-π-acceptor (D2-D-π-A) and (acceptor)₂-donor-π-acceptor (A2-D-π-A) organic photosensitizers based on the framework of (Z)-2-cyano-3-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)acrylic acid have been synthesized and characterized. By incorporating groups with different electron-donating or withdrawing abilities, such as dibenzothiophene (DBT), dibenzofuran (DBF), and triazine (TA), into the triphenylamine segment, their photophysical properties have been regulated. Theoretical calculations were used to explore how various donor-acceptor combinations influence their hydrogen production performance.
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