This review article summarizes recent progress in the synthesis and optoelectronic properties of conjugated materials containing heavy main group elements from Group 13-16 as integral components. As will be discussed, the introduction of these elements can promote novel phosphorescent behavior and support desirable molecular and polymeric properties such as low optical band gaps and high charge mobilities for photovoltaic and thin film transistor applications.

The PBP ligand (Ph2PC6H4)2BPh was used to prepare ((Ph2PC6H4)2B(Cl)(η(6)-Ph)RuCl (1) and subsequently [((Ph2PC6H4)2B(η(6)-Ph))RuCl][B(C6F5)4] (2). The latter species exhibited Lewis acidity on the η(6)-Ph ring, as reaction with Cy3P gave the donor-acceptor adduct [(Ph2PC6H4)2B(η(5)-C6H5-o-PCy3)RuCl][B(C6F5)4] (3). Steric frustration of this binding was seen with Mes3P, and yet the combination of 2 and Mes3P reacted with H2 to give a 2:1 mixture of 5-o and 5-p, two isomers of [(Ph2PC6H4)2B(η(5)-C6H6)RuCl] (5), along with [Mes3PH][HB(C6F5)3]. Compound 2 behaves as C-based Lewis acid and thus can also be used for catalytic hydrogenation of aldimines at room temperature via a frustrated Lewis pair mechanism.

The synthesis of the first bismuth‐containing macromolecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (>300 kDa) feature benzobismoles appended to a hydrocarbon scaffold, and were built via an efficient ring‐opening metathesis (ROMP) protocol. Moreover, our general procedure readily allows for the formation of cross‐linked networks and block copolymers. Attaining stable red phosphorescence with non‐toxic elements remains a challenge and, thus, our new class of soluble (processable) polymeric phosphor is of great interest. Furthermore, the formation of bismuth‐rich cores within organic–inorganic block copolymer spherical micelles is possible, leading to patterned arrays of bismuth in the film state.

The combination of (indenyl)Ru(PPh 3 ) 2 (CCPh) (1) with B(C 6 F 4 H) 3 or Al(C 6 F 5 ) 3 generates FLPs that are shown to react with CO 2 , aldehyde, and alkyne to generated new C−C bonds. While in these reactions the metal center is ancillary, subsequent reaction of the alkyne addition product with additional alkyne prompts Ru vinylidene chemistry that releases the new organic fragment from Ru.

The reactions of gold-acetylides with B(C 6 F 5 ) 3 afford alkynyl borate species and cationic π-coordinated gold complexes. The analogous reactions with aryl gold species generate gem-diaurated compounds containing a borate counteranion. These new σ-B/π-Au alkynyl borate complexes can be employed as active catalysts in homogeneous catalysis and represent a new silver-free activation pathway. The new alkynyl borate species are fully characterized, and the alkyne fragments are shown to be bound in a σ-B/π-Au fashion. Upon prolonged heating, these compounds undergo a slow C 6 F 5 group transfer to gold affording LAuC 6 F 5 species.

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Previous research in our group showed that tellurophenes with pinacolboronate (BPin) units at the 2- and/or 5-positions displayed efficient phosphorescence in the solid state, both in the presence of oxygen and water. In this current study, we show that luminescence from a tellurophene is possible when various aryl-based substituents are present, thus greatly expanding the family of known (and potentially accessible) Te-based phosphors. Moreover, for the green phosphorescent perborylated tellurium heterocycle, 2,3,4,5-TeCBPin (4BTe), oxygen-mediated quenching of phosphorescence is an important contributor to the lack of emission in solution (when exposed to air); thus, this system displays aggregation-enhanced emission (AEE). These discoveries should facilitate the future design of color tunable tellurium-based luminogens.

Br) react with the ancillary ligand O(CH 2 CH 2 PCy 2 ) 2 to yield the alkylidene species (POP-Cy)RuX 2 (CHPh) (X = Cl 1, Br 2). Subsequent reaction of 1 and 2 with GaX 3 generates the alkylidyne hydride salts [(POP-Cy)RuHX(CPh)][GaX 4 ] (X = Cl 3, Br 4). Treatment of 3 and 4 with the donor ligand pyridine converts these alkylidyne hydrides to the Rualkylidene complexes [(POP-Cy)Ru(py)X(CHPh)][GaX 4 ] (X = Cl 5, Br 6). The complexes 5 and 6 are also formed directly by addition of the Lewis acid-base adduct (py)GaX 3 to 1 and 2, respectively. The alkylidyne hydride species 3 and 4 are also quantitatively converted back to alkylidene species 1 and 2 by addition of excess Bu 4 NX (X = Cl, Br), respectively. Similarly treatment of 5 and 6 with [Et 3 NH]X or [Bu 4 N]X (X = Cl, Br) resulted in the re-formation of 1 and 2. These data demonstrate that the interconversion of alkylidene and alkylidyne hydride is energetically facile. This view is supported by crystallographic and preliminary DFT data.