Publications
2014-2017
Direct C-metallation of N-substituted Triazoles Promoted by Mercury acetate. An alternative route to N-heterocyclic carbene complexes. Nai-Chieh Lin, Herbert J. H. Syu*, Abbas Raja Naziruddin, Fu-Chen Liu* and Ivan J. B. Lin*, RSC Adv. 2017, 7, 11652-11656
(DOI: 10.1039/C7RA00163K​)
C–Metallation of neutral mono-substituted triazoles could be induced by Hg(OAc)2 to give a near quantitative yield of C,N-bonded mercury complexes. Initial N–coordination to mercury(II) is confirmed by NMR spectroscopy. Subsequent acetate assisted deprotonation–metallation is a viable route to C–metalated products. Hg(OAc)2 is unique for this reaction. Metal salts of Ag2O, Ag(OAc), Pd(OAc)2 or HgCl2 in combination with bases of NaOH and K2CO3 did not yield triazolate complexes. Further reaction of one of these mercury(II)–C,N-triazolate complexes with a source of methyl cation yielded a monomeric N–heterocyclic carbene complex. Therefore the facile reaction of triazole with Hg(OAc)2 followed by alkylation is a handy alternative way to prepare Hg–NHCs.
Formation of NH,NR N-Heterocyclic Carbene Complexes through Mercuration of Mono-N-substituted Benzimidazoles. Ming-Hung Yu, Hsueh-Hui Yang, Abbas Raja Naziruddin, Shanker Kanne, Bo-Han Wang, Fu-Chen Liu*, Ivan J. B. Lin, Gene-Hsiang Lee, Eur. J. Inorg. Chem. 2016, 29, 4829–4834
(DOI: ​10.1002/ejic.201600759)
The reactions of N-substituted benzimidazoles (R-Bim) with Hg(OAc)2 in the presence of NaBr produces N- and C-bound 12-membered mercuramacrocycles [Hg4(R-Bim)4Br4] [R = Me, pyridyl (Py), Bn]. The further protonation of these mercuramacrocycles with HBF4·OEt2 produced NH,NR N-heterocyclic carbene (NHC) complexes [(R-BimH)2Hg][BF4]2.
Platinum Complexes Bearing Normal and Mesoionic N-Heterocyclic Carbene Based Pincer Ligands: Syntheses, Structures, and Photo-Functional Attributes. Abbas Raja Naziruddin, Chen-Shiang Lee, Wan-Jung Lin, Bing-Jian Sun, Kang-Heng Chao, Agnes Hsiu Hwa Chang*, Wen-Shu Hwang*, Dalton Trans. 2016, 45, 5848-5859
(DOI: ​10.1039/C5DT04770F)
Platinum Complexes featuring pyridine bis-N-heterocyclic imidazol-2-ylidene or triazol-5-ylidene are prepared with different auxiliary ligands. This report summarizes their structures, photo-physics and electrochemical details. Vapo/mechanochromic emission responses have also been detected.
Correlating Structural and Photophysical Features of Pincer Luminophores and Monodentate Ancillary Ligands in Pt (II) Phosphors. Anzhela Galstyan, Abbas Raja Naziruddin, Cristina Cebrián, Adriana Iordache, Constantin G. Daniliuc, Luisa De Cola*, Cristian A. Strassert*, Eur. J. Inorg. Chem. 2015, 36, 5822-5831
(DOI: ​10.1002/ejic.201500949)
Phosphorescent PtII complexes featuring pincer luminophores of 2,6-bis(1,2,4-triazolyl)pyridine and 2,6-bis(pyrazolyl)pyridine with bulky adamantyl or tolyl substituents are systematically compared, and their structural features are correlated with their photophysical properties.
Photofunctional Platinum Complexes Featuring N-Heterocyclic Carbene-Based Pincer Ligands. Wan-Jung Lin, Abbas Raja Naziruddin, Yu-Hsuan Chen, Bian Jian Sun, A. Hsiu-Hwa-Chang, Wen-Jwu Wang and Wen-Shu Hwang*, Chem. Asian J. 2015, 10, 728-739
(DOI: ​10.1002/asia.201403306)
Have fun, be active: Photoactive platinum complexes of pincer-bis-N-heterocyclic-carbenes, [(RCCCR)Pt-L] (R=Me, nBu; L=-CN, -C≡CPh, -N≡CCH3, -Py, -CO; and [(MeCCCMe)Pt-Cl] showing emission changes upon exposure to small molecules or mechanical triggers are reported.
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Bidentate NHC^pyrozolate Ligands in Luminescent Platinum(II) Complexes. Abbas Raja Naziruddin, Anzhela Galstyan, Adriana Iordache, Constantin G. Daniliuc, Cristian A. Strassert*, Luisa De Cola*, Dalton Trans. 2015, 44, 8467-8477
(DOI: ​10.1039/C4DT03651D)
Platinum complexes containing NHC^pyrozolate ligands and functionalized-phenyl-pyridine or triazole-pyridineAd chromophores are reported. All the compounds are luminescent and their emission can be tuned from blue to yellow.
Donor Functionalized Ruthenium N-Heterocyclic Carbene Complexes in Alcohol Oxidation Reactions. Abbas Raja Naziruddin, Chun-Shiuan Zhuang, Wan-Jung Lin, Wen-Shu Hwang*, Dalton Trans. 2014, 43, 5335-5342
(DOI: ​10.1039/C3DT53125B)
N-Pyridyl, N′-amido functionalized imidazolium bromides were obtained in high yields as an N-heterocyclic carbene (NHC) precursor and used as bidentate or a pincer ligands to obtain ruthenium complexes via a silver NHC transmetallation route. The incorporation of a phenyl group as an amido-N substituent (R = Ph) results in a bidentate coordination mode through the CNHC and Npyridyl donors, whereas in its absence (R = H) a pincer coordination mode was observed through the Npyridyl^CNHC^Oamido donors. The ruthenium complex featuring a pincer type NCO coordination mode with a protic NH function adjacent to the coordinating Oamido atom was found to efficiently catalyse the oxidation of activated alcohols effecting quantitative conversions within 30 minutes. However the oxidation of deactivated alcohols required longer reaction times to effect the quantitative transformation.
Ruthenium Complexes Bearing Unsymmetric CNC’ Pincer Ligands: Molecular Structures and Electronic Properties. Abbas Raja Naziruddin, Chia-Liang Kuo, Wan-Jung Lin, Wei-Hao Lo, Chen-Shiang Lee, Bian-Jian-Sun, A. Hsiu Hwa Chang, Wen-Shu Hwang*, Organometallics 2014, 33, 2575-2582
(DOI: ​10.1021/om500205p)
Homoleptic ruthenium complexes [Ru(Ln)2] bearing unsymmetric pyridine-based bis N-heterocyclic carbene (NHC) pincer ligands are synthesized and structurally characterized. These complexes feature the coexistence of a five-membered and a six-membered ruthenacycle within the same ligand framework, allowing an ideally octahedral CNHC–Ru–NPy bite angle close to 90°. In the solid state, impressive MLCT lifetimes of microsecond regime were detected in all of the complexes, of which [Ru(L4)2] , featuring four benzimidazol-2-ylidene donors, exhibited the longest values. Electronic properties of all of the ruthenium complexes are investigated by cyclic voltammetry and spectroscopic techniques. Density functional theory results were used to support the experimental observations.
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