Syntheses, Structures and Photophysical Properties of Metal Carbonyl Clusters with Dansyl and Acridone Luminophores

Abstract

A series of fluorescent transition metal complexes bearing the 5-(dimethylamino)naphthalene-1-sulfonyl (R 1 ) and acridone (R 2 ) frameworks have been prepared. Reactions of the fluorescent-labeled alkyne ligands R 1 CH 2 CϵCH and R 2 CH 2 CϵCH with various metal carbonyl compounds [Co 2 (CO) 8 ],[Et 3 NH][Fe 2 (CO) 6 (µ-CO)(µ-StBu)] and [M 3 (CO) 10 (NCMe) 2 ] (M = Ru, Os) readily afforded new cluster complexes of the stoichiometry [Co 2 (CO) 6 (µ-η 2 -RCH 2 CCH)] (1: R = R 1 , 2: R 2 ), [Fe 2 (CO) 6 (µ-StBu)(µ-η 2 -RCH 2 C=CH 2 )] (3: R = R 1 , 4: R 2 ), [Ru 3 (CO) 9 (µ-CO)(µ 3 -η 2 -RCH 2 CCH)] (5: R = R 1 , 6: R 2 ) and [Os 3 (CO) 9 (µ-CO)(µ 3 -η 2 -RCH 2 CCH)] (7: R = R 1 , 8: R 2 ) in moderate to good yields. All of these new complexes have been fully characterized by

Post‐Modification of Organoiron Poly(alkynyl methacrylate)s with Dicobalt Hexacarbonyl

“…XRD analysis of 14 (Figure 5, Table 1) shows coordination of each of the cobalt atoms to the acetylene carbons. This butterfly complex is similar to typical M 2 L 6 ‐acetylenes35–38 and shows a nearly linear dihedral C21–Co1–Co2–C24 angle (6°) and a Co–Co bond length of 2.48 Å that lie within normal range for this type of structure. The bulkiness of the cobalt carbonyl cluster forces the rest of the molecule into what is essentially a cis conformation at the acetylene moiety, leaving the methylene carbons (C15 and C12) and ester atoms in a parallel orientation, where they are nearly in the same plane.…”

Synthesis, photochemistry, and electrochemistry of ruthenium(II) polypyridyl complexes anchored by dicobalt carbonyl units

“…Interestingly, such a phosphorescent band has hardly been detected for RuCo 2 complexes 1 and 2 by our commercial emission spectrophotometer. To the best of our knowledge, this kind of behavior has not previously been reported for heteronuclear metal complexes linked with dicobalt carbonyl units, although emission quenching has been reported for a few examples of fluorescent organic compounds, including dicobalt carbonyl complex [24]. The emission quenching for Ru-Co 2 hybrid complexes indicates that the photoexcited state of this Ru-Co 2 system is susceptible to efficient intramolecular energy transfer from the ruthenium polypyridyl unit to the dicobalt carbonyl unit and then leads to the ground state by a radiationless deactivation accompanied by a vibrational relaxation of the dicobalt carbonyl unit.…”

Fluorescent tags. dansyl amide (CH3)2N–С10Н6–SO2NH2: Reflection of the conformational properties of a free molecule in crystal structures

“…They include diverse Х substituents, such as N-2-aminoethyl, N-benzyl, glycine, N-N′-benzene-1,2-diamine, 2-propyl, etc. [3,4,6,8,9]. 41 structures of the mentioned moiety were found, in which two C6-C5-N-C11 and C6-C5-N-C12 torsion angles determining the position of the -N(CH 3 ) 2 group relative to the naphthalene core take values within the ranges of -104°--113° and 13°-25° or 104°-113° and -13°--25°, which are close to the values of the corresponding angles in the conformers and enantiomers of the dansyl amide molecule (Table 1).…”

“…However, the crystal structures of some complicated organic and complex compounds have been known [4][5][6][7][8][9] whose composition contains dansyl amide as a substituent or a part of the ligand. In different crystals the -SO 2 NH-group of the dansyl amide molecule can take a different spatial position with respect to the naphthalene core plane [4,9], and moreover, a different mutual orientation of -(CH 3 ) 2 N and -SO 2 NH groups is possible [4,5,9]. From the analysis of X-ray crystallographic data it follows that the environment of dansyl amide (CH 3 ) 2 N-C 10 Н 6 -SO 2 NH-in the crystal strongly affects its geometric structure and makes ambiguous its conformational properties.…”