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1. Studies of spin related processes in fullerene C ₆₀ devices

   https://doi.org/10.1039/C7TC05086K  

   Liu, Haoliang; Wang, Jingying; Groesbeck, Matthew; Pan, Xin; Zhang, Chuang; Vardeny, Z. Valy (January 2018, Journal of Materials Chemistry C)

   We have investigated spin related processes in fullerene C 60 devices using several experimental techniques, which include magnetic field effect of photocurrent and electroluminescence in C 60 -based diodes; spin polarized carrier injection in C 60 -based spin-valves; and pure spin current generation in NiFe/C 60 /Pt trilayer devices. We found that the ‘curvature-related spin orbit coupling’ in C 60 plays a dominant role in the obtained spin-related phenomena. The measured magneto-photocurrent and magneto-electroluminescence responses in C 60 diodes are dominated by the difference in the g -values of hole and electron polarons in the fullerene molecules. We also obtained giant magneto-resistance of ∼10% at 10 K in C 60 spin-valve devices, where spin polarized holes are injected into the C 60 interlayer. In addition, using the technique of spin-pumping in NiFe/C 60 /Pt trilayer devices with various C 60 interlayer thicknesses we determined the spin diffusion length in C 60 films to be 13 ± 2 nm at room temperature. 

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2. Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtCCCCCCCC] _m PtX segments; iterative syntheses and functionalization for measurements of single molecule properties

   https://doi.org/10.1039/C9DT00870E  

   Zheng, Qinglin; Schneider, Jakob F.; Amini, Hashem; Hampel, Frank; Gladysz, John A. (April 2019, Dalton Transactions)

   Reaction of ( p -tol 3 P) 2 PtCl 2 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/THF/reflux) gives monosubstituted trans -Cl( p -tol 3 P) 2 Pt(CC) 2 SiMe 3 (63%), which with wet n -Bu 4 N + F − yields trans -Cl( p -tol 3 P) 2 Pt(CC) 2 H ( 2 , 96%). Hay oxidative homocoupling (O 2 /CuCl/TMEDA) gives all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 Cl ( 3 , 68%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/rt) affords monosubstituted all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (46%), which is converted by a similar desilylation/homocoupling sequence to all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 3 Pt(P p -tol 3 ) 2 Cl ( 7 ; 79%). Reaction of ( p -tol 3 P) 2 PtCl 2 and excess H(CC) 2 SiMe 3 (HNEt 2 /cat. CuI) gives trans -Me 3 Si(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (78%), which with wet n -Bu 4 N + F − affords trans -H(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Hay oxidative cross coupling with 2 (1 : 4) gives all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 2 Pt(P p -tol 3 ) 2 Cl ( 10 , 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 2/rt) yields all- trans -Me 3 Si(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 ( 17 , 77%), which with wet n -Bu 4 N + F − gives all- trans -H(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Reaction of 3 and excess Me 3 P gives all- trans -Cl(Me 3 P) 2 Pt(CC) 4 Pt(PMe 3 ) 2 Cl ( 4 , 86%). A model reaction of trans -( p -tol)( p -tol 3 P) 2 PtCl and KSAc yields trans -( p -tol)( p -tol 3 P) 2 PtSAc ( 12 , 75%). Similar reactions of 3 , 7 , 10 , and 4 give all- trans -AcS[(R 3 P) 2 Pt(CC) 4 ] n Pt(PR 3 ) 2 SAc (76–91%). The crystal structures of 3 , 17 , and 12 are determined. The first exhibits a chlorine–chlorine distance of 17.42 Å; those in 10 and 7 are estimated as 30.3 Å and 43.1 Å. 

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3. A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages

   https://doi.org/10.1038/s41467-022-34651-5  

   Meng, Qingyu; Abella, Laura; Yao, Yang-Rong; Sergentu, Dumitru-Claudiu; Yang, Wei; Liu, Xinye; Zhuang, Jiaxin; Echegoyen, Luis; Autschbach, Jochen; Chen, Ning (December 2022, Nature Communications)

   Abstract Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@C_s(6)-C₈₂and UN@C₂(5)-C₈₂, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@C_s(6)-C₈₂and UN@C₂(5)-C₈₂. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)²⁺@(C₈₂)²⁻electronic structure with formal +5 oxidation state (f¹) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species. 

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4. Identification of the structure of the Bi promoted Pt non-oxidative coupling of methane catalyst: a nanoscale Pt ₃ Bi intermetallic alloy

   https://doi.org/10.1039/C8CY02171F  

   Zhu Chen, Johnny; Wu, Zhenwei; Zhang, Xiaoben; Choi, Slgi; Xiao, Yang; Varma, Arvind; Liu, Wei; Zhang, Guanghui; Miller, Jeffrey T. (March 2019, Catalysis Science & Technology)

   Recently, stable non-oxidative conversion of methane (NOCM) for up to 8 h with a C 2 selectivity greater than 90% has been reported over Pt–Bi/ZSM-5 at moderate temperatures (600–700 °C). In this study, we show that the structure of the bimetallic nanoparticles on Pt–Bi/ZSM-5 catalyst is similar to Pt–Bi/SiO 2 . EXAFS indicates the formation of Pt-rich bimetallic Pt–Bi nanoparticles with Pt–Bi bond distance of 2.80 Å. The XRD spectra (on SiO 2 ) are consistent with cubic, intermetallic surface Pt 3 Bi phase on a Pt core. The Pt 3 Bi structure is not known in the thermodynamic phase diagram. In all catalysts, only a small fraction of Bi alloys with Pt. At high Bi loadings, excess Bi reduces at high temperature, covering the catalytic surface leading to a loss in activity. At lower Bi loadings with little excess Bi, the Pt 3 Bi surface is effective for non-oxidative coupling of CH 4 (on ZSM-5) and propane dehydrogenation (on SiO 2 ). 

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5. Platinum( ii ) alkyl complexes of chelating dibridgehead diphosphines P((CH ₂ ) _n ) ₃ P ( n = 14, 18, 22); facile cis / trans isomerizations interconverting gyroscope and parachute like adducts

   https://doi.org/10.1039/D1DT02321G  

   Zhu, Yun; Ehnbom, Andreas; Fiedler, Tobias; Shu, Yi; Bhuvanesh, Nattamai; Hall, Michael B.; Gladysz, John A. (September 2021, Dalton Transactions)

   The gyroscope like dichloride complexes trans -Pt(Cl) 2 (P((CH 2 ) n ) 3 P) ( trans -2; n = c, 14; e, 18; g, 22) and MeLi (2 equiv.) react to yield the parachute like dimethyl complexes cis -Pt(Me) 2 (P((CH 2 ) n ) 3 P) ( cis -4c,e,g, 70–91%). HCl (1 equiv.) and cis -4c react to give cis -Pt(Cl)(Me)(P((CH 2 ) 14 ) 3 P) ( cis -5c, 83%), which upon stirring with silica gel or crystallization affords trans -5c (89%). Similar reactions of HCl and cis -4e,g give cis / trans -5e,g mixtures that upon stirring with silica gel yield trans -5e,g. A parallel sequence with trans -2c/EtLi gives cis -Pt(Et) 2 (P((CH 2 ) 14 ) 3 P) ( cis -6c, 85%) but subsequent reaction with HCl affords trans -Pt(Cl)(Et)(P((CH 2 ) 14 ) 3 P) ( trans -7c, 45%) directly. When previously reported cis -Pt(Ph) 2 (P((CH 2 ) 14 ) 3 P) is treated with HCl (1 equiv.), cis - and trans -Pt(Cl)(Ph)(P((CH 2 ) 14 ) 3 P) are isolated (44%, 29%), with the former converting to the latter at 100 °C. Reactions of trans -5c and LiBr or NaI afford the halide complexes trans -Pt(X)(Me)(P((CH 2 ) 14 ) 3 P) ( trans -9c, 88%; trans -10c, 87%). Thermolyses and DFT calculations that include acyclic model compounds establish trans > cis stabilities for all except the dialkyl complexes, for which energies can be closely spaced. The σ donor strengths of the non-phosphine ligands are assigned key roles in the trends. The crystal structures of cis -4c, trans -5c, trans -7c, and trans -10c are determined and analyzed together with the computed structures. 

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