Synthesis and Characterization of Photothermal Osmium Carbolong Complexes

Abstract

Metallacycles with chelating polydentate conjugated-carbon chain ligands are called carbolong complexes, which are expected to have interesting properties. In this work, the preparation of 12-carbon carbolong complexes in which all of the coordinated atoms in the equatorial plane are carbon atoms was studied. With the help of the well-established mechanism, a new approach to prepare coplanar carbolong complexes bearing different organic functional groups was developed by adding different terminal alkynes in sequence. In the presence of HBF , these coplanar carbolong complexes were converted to η -allyl osmapentalene derivatives, which can be produced directly from the reaction of cyclopropaosmapentalene 1 with terminal alkynes in the presence of AgBF under anhydrous conditions. This study offers a new route for the preparation of functional osmium carbolong complexes with excellent photothermal properties, which can be used to prepare photothermal materials.

Metallaaromatic Chemistry: History and Development

“…In the presence of H 2 O, this byproduct could be extracted from the organic reactant phase, or else it would further react with 806 to give the η 3 -allyl osmapentalene derivative 807 (Scheme 259). 542 Alternatively, H 2 O can be replaced by other acid scavengers, such as N-methyldiphenylamine. 542 Mechanistically, complex 806 results from the step-by-step insertion of two molecules of phenylacetylene into the Os−C(sp 3 ) bond, which was confirmed by the isolation of some analogues of 806 originating from 13 with two different alkynes, although the monoinsertion intermediate could not be isolated.…”

“…542 Alternatively, H 2 O can be replaced by other acid scavengers, such as N-methyldiphenylamine. 542 Mechanistically, complex 806 results from the step-by-step insertion of two molecules of phenylacetylene into the Os−C(sp 3 ) bond, which was confirmed by the isolation of some analogues of 806 originating from 13 with two different alkynes, although the monoinsertion intermediate could not be isolated. Moreover, deuterium labeling experiments and the reaction of 13 with 3hexyne, have been carried out to further understand the mechanism.…”

Optically reconfigurable shape memory metallo-polymer mediated by a carbolong complex and radically exchangeable covalent bond

“…The carbolong complex (denoted CLC556, Scheme 1a) used here is a metal bridgehead polycyclic framework featuring a long carbon chain (≥7C) coordinated to a metal via metalcarbon bonds 35,36 and has been demonstrated to be an excellent NIR-responsive photothermal conversion moiety. [37][38][39][40][41][42] The hydroxyl functionalized carbolong complex compound 1 was synthesized according to the published procedure. 37 1-(2-Hydroxy-1-phenylethoxy)-2,2,6,6-tetramethylpiperidin-4-ol (compound 2), containing a radically exchangeable TEMPObased alkoxyamine moiety (denoted TEMPO-C), was synthesized in two steps from commercially available materials (Scheme S1 †).…”

Cylindrical NIR-Responsive Metallopolymer Containing Möbius Metalla-aromatics

“…Metalla-aromatics constructed with at least one metal and conjugated carbon-framework(s) are very interesting and valuable materials due to their aromatic system. , Most of these materials have excellent thermodynamic stability and display the properties of both aromatic compounds and organometallics. For example, the reactivity of metallabenzene (a well-known metalla-aromatics) is similar to those of benzene (e.g., electrophilic aromatic substitution) and dialkyl organometallics (e.g., reductive elimination). , We have recently developed a type of brand-new highly conjugated Craig-type Möbius metalla-aromatics, − in which the transition metals were chelated with “carbolongs”. , Depending on their specific structures, these “carbolong complexes” , could show different properties, including light absorption or emission ability, J -aggregates behavior, single-molecular conductivity, photothermal conversion, ,,,,, and photoacoustic imaging capability. , …”

“…3,4 We have recently developed a type of brand-new highly conjugated Craig-type Mobius 5 metalla-aromatics, 6−12 in which the transition metals were chelated with "carbolongs". 12,13 Depending on their specific structures, these "carbolong complexes" 14,15 could show different properties, including light absorption 16 or emission 17 ability, J-aggregates behavior, 18 single-molecular conductivity, 19 photothermal conversion, 8,12,14,18,20,21 and photoacoustic imaging capability. 8,21 Among these properties, photothermal conversion is the most important for carbolong complexes.…”