Interactions of the known compounds Ir(q-C5Me5)(NR) (R = But l a or 2,6-Pri&H3 lb) with 2,6-xylyl isocyanide [(xyl)NC], mesityl isocyanate and mesityl a i d e (mesityl = mes = C,H2Me3-2,4,6) have been studied. The bridged dimers [Ir(q -C Me ,)( p-NC H,)] 2 and [Ir,(q -C , Me , ) 2( p-NC6H ')(p-NHC,H 1)] C1 3 have been synthesized. Reactions of Ru(NR')(MeC,H,Pr'-p) (R' = 2,4,6-But3C,H2) with (mes)NCO and (mes)N, are reported. Attempts to isolate Rh(q-C,Me,)(NR) species failed but evidence for Rh(q-C,Me,)m(2,6-Pr',C,H,)N3(mes)] was obtained in a trapping reaction in solution using (mes)N,. The crystal structures of the compounds Ir(q -C , Me &q ' -Bu'NCNBu')(CNBu'), [Ir(q -C H ,)(p-NC, H,)] 2,3, [Ir2(q-CSMeS)(p-NC6Hl 1)(p-NHC6H, l)]Cl 3, Ir(q-C,Me,)~(xyl)CHN(2,6-Pri2C6H3)CNC,H3(Me)CH2] 4b, Ir(q-C,Me,)~(2,6-Pr',C,H3)C(0)N(mes)] 5, Ir(q-C,Me,)~(2,6-Pr',C,H3)N3(mes)] 6, Rum(2,4,6-BU'~C~H~)C(O)N(~~~S)](M~C,H,P~'-~) 8 and Ru~(2,4,6-Bu',C,H2)N,(mes)](MeC,H,Pri-p) 9 have been

precursors, [4] doping proves challenging for solution-synthesized MC nanostructures. [5] Recently, post-synthesis halide treatment of nanocrystals in solution has been developed which involves switching halogens for long chain surfactant molecules absorbed on the surface. [2,6] In fact, sorption of halogens can be realized as part of a one-pot synthesis using metal halide precursors. [7] Although this strategy was initially developed for passivation of MC quantum dots against oxidation, [2,6,7] annealing or hot pressing halogen-coated nanoparticles allows halides to diffuse into the MC lattice and substitute for chalcogenide anions. [8] However, controlling doping levels is not straightforward and such methods can introduce rather high halide concentrations in small nanocrystals leading to reduced electrical conductivity. [8b] Hence exerting control over dopant concentration without sacrificing electrical performance is imperative.Thermoelectrics realize direct interconversion between thermal and electric energy, thus providing an important route An aqueous solution method is developed for the facile synthesis of Cl-containing SnSe nanoparticles in 10 g quantities per batch. The particle size and Cl concentration of the nanoparticles can be efficiently tuned as a function of reaction duration. Hot pressing produces n-type Cl-doped SnSe nanostructured compacts with thermoelectric power factors optimized via control of Cl dopant concentration. This approach, combining an energy-efficient solution synthesis with hot pressing, provides a simple, rapid, and low-cost route to high performance n-type SnSe thermoelectric materials.Doping plays a vital role in modifying the electronic properties of semiconductors and is pivotal for (opto)electronics, [1] photovoltaics (PV), [2] and thermoelectrics. [3] Metal chalcogenides (MCs) form a diversity of functional materials well-suited to such applications. Halogen doping in MCs has proven effective to realize n-type conducting behavior and tune carrier concentrations. [2][3][4] Enhanced thermoelectric and PV performance can result. [2][3][4] While halogens can be readily doped into bulk MCs by high-temperature synthesis using metal halide

A surfactant‐free solution methodology, simply using water as a solvent, has been developed for the straightforward synthesis of single‐phase orthorhombic SnSe nanoplates in gram quantities. Individual nanoplates are composed of {100} surfaces with {011} edge facets. Hot‐pressed nanostructured compacts (E g≈0.85 eV) exhibit excellent electrical conductivity and thermoelectric power factors (S 2 σ) at 550 K. S 2 σ values are 8‐fold higher than equivalent materials prepared using citric acid as a structure‐directing agent, and electrical properties are comparable to the best‐performing, extrinsically doped p‐type polycrystalline tin selenides. The method offers an energy‐efficient, rapid route to p‐type SnSe nanostructures.

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