{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T20:05:19Z","timestamp":1791144319525,"version":"4.1.0"},"reference-count":95,"publisher":"Wiley","issue":"41","license":[{"start":{"date-parts":[[2009,9,23]],"date-time":"2009-09-23T00:00:00Z","timestamp":1253664000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,10,19]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The complexes [Au\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    ][X]\n                    <jats:sub>3<\/jats:sub>\n                    {dcmp=bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X=Cl\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>1<\/jats:bold>\n                    ), ClO\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>2<\/jats:bold>\n                    ), OTf\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>3<\/jats:bold>\n                    ), PF\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>4<\/jats:bold>\n                    ), SCN\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:bold>5<\/jats:bold>\n                    )}, [Ag\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    ][ClO\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sub>3<\/jats:sub>\n                    (\n                    <jats:bold>6<\/jats:bold>\n                    ), and [Ag\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    ][ClO\n                    <jats:sub>4<\/jats:sub>\n                    ] (\n                    <jats:bold>7<\/jats:bold>\n                    ) were prepared and their structures were determined by X\u2010ray crystallography. Complexes\n                    <jats:bold>2<\/jats:bold>\n                    \u2013\n                    <jats:bold>4<\/jats:bold>\n                    display a high\u2010energy emission band with\n                    <jats:italic>\u03bb<\/jats:italic>\n                    <jats:sub>max<\/jats:sub>\n                    at 442\u2013452\u2005nm, whereas\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>5<\/jats:bold>\n                    display a low\u2010energy emission with\n                    <jats:italic>\u03bb<\/jats:italic>\n                    <jats:sub>max<\/jats:sub>\n                    at 558\u2013634\u2005nm in both solid state and in dichloromethane at 298\u2005K. The former is assigned to the\n                    <jats:sup>3<\/jats:sup>\n                    [5d\u03c3*6p\u03c3] excited state of [Au\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>3+<\/jats:sup>\n                    , whereas the latter is attributed to an exciplex formed between the\n                    <jats:sup>3<\/jats:sup>\n                    [5d\u03c3*6p\u03c3] excited state of [Au\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>3+<\/jats:sup>\n                    and the counterions. In solid state, complex [Ag\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    ][ClO\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sub>3<\/jats:sub>\n                    (\n                    <jats:bold>6<\/jats:bold>\n                    ) displays an intense emission band at 375\u2005nm with a Stokes shift of \u22487200\u2005cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    from the\n                    <jats:sup>1<\/jats:sup>\n                    [4d\u03c3*\u21925p\u03c3] absorption band at 295\u2005nm. The 375\u2005nm emission band is assigned to the emission directly from the\n                    <jats:sup>3<\/jats:sup>\n                    [4d\u03c3\n                    <jats:sup>*<\/jats:sup>\n                    5p\u03c3] excited state of\n                    <jats:bold>6<\/jats:bold>\n                    . Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (\n                    <jats:italic>n<\/jats:italic>\n                    ) in polynuclear Au\n                    <jats:sup>I<\/jats:sup>\n                    and Ag\n                    <jats:sup>I<\/jats:sup>\n                    linear chain complexes without close metal\u22c5\u22c5\u22c5anion contacts. The emission energies are extrapolated to be 715 and 446\u2005nm for the infinite linear Au\n                    <jats:sup>I<\/jats:sup>\n                    and Ag\n                    <jats:sup>I<\/jats:sup>\n                    chains, respectively, at metal\u22c5\u22c5\u22c5metal distances of about 2.93\u20133.02\u2005\u00c5. A QM\/MM calculation on the model [Au\n                    <jats:sub>3<\/jats:sub>\n                    (dcmp)\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    system, with Au\u22c5\u22c5\u22c5Cl contacts of 2.90\u20133.10\u2005\u00c5, gave optimized Au\u22c5\u22c5\u22c5Au distances of 2.99\u20133.11\u2005\u00c5 in its lowest triplet excited state and the emission energies were calculated to be at approximately 600\u2013690\u2005nm, which are assigned to a three\u2010coordinate Au\n                    <jats:sup>I<\/jats:sup>\n                    site with its spectroscopic properties affected by Au\n                    <jats:sup>I<\/jats:sup>\n                    \u22c5\u22c5\u22c5Au\n                    <jats:sup>I<\/jats:sup>\n                    interactions.\n                  <\/jats:p>","DOI":"10.1002\/chem.200901757","type":"journal-article","created":{"date-parts":[[2009,9,23]],"date-time":"2009-09-23T13:01:14Z","timestamp":1253710874000},"page":"10777-10789","source":"Crossref","is-referenced-by-count":76,"title":["The\n                    <sup>3<\/sup>\n                    [\n                    <i>n<\/i>\n                    d\u03c3*(\n                    <i>n<\/i>\n                    +1)p\u03c3] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands"],"prefix":"10.1002","volume":"15","author":[{"given":"Glenna\u2005So\u2005Ming","family":"Tong","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Steven\u2005Chi\u2005Fai","family":"Kui","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hsiu\u2010Yi","family":"Chao","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nianyong","family":"Zhu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chi\u2010Ming","family":"Che","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,10,13]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/c29700001124"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00028a013"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.11.015"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b716650h"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.11.026"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/a804249g"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9920003325"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00310a026"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960109i"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990712)111:13\/14<2083::AID-ANGE2083>3.0.CO;2-4"},{"key":"e_1_2_7_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990712)38:13\/14<1979::AID-ANIE1979>3.0.CO;2-M"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990917)111:18<2953::AID-ANGE2953>3.0.CO;2-J"},{"key":"e_1_2_7_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990917)38:18<2783::AID-ANIE2783>3.0.CO;2-I"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20011105)7:21<4656::AID-CHEM4656>3.0.CO;2-D"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)90025-X"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200204610"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp049873w"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971091109"},{"key":"e_1_2_7_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199711791"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja012397s"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja020902v"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200305657"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja973216i"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/a802805b"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00240-X"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19981016)110:20<3041::AID-ANGE3041>3.0.CO;2-E"},{"key":"e_1_2_7_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19981102)37:20<2857::AID-ANIE2857>3.0.CO;2-G"},{"key":"e_1_2_7_24_2","first-page":"1028","author":"Yam V. 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The optimized triplet state geometries and the photophysical data obtained at these geometries are given in the Supporting Information."},{"key":"e_1_2_7_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja036508u"},{"key":"e_1_2_7_86_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.10156"},{"key":"e_1_2_7_87_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.447079"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00051a040"},{"key":"e_1_2_7_89_2","unstructured":"Gaussian\u200503 Revision B.05 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery\u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. 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Pittsburgh PA 2004."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200901757","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200901757","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T17:07:14Z","timestamp":1760288834000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200901757"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,10,13]]},"references-count":95,"journal-issue":{"issue":"41","published-print":{"date-parts":[[2009,10,19]]}},"alternative-id":["10.1002\/chem.200901757"],"URL":"https:\/\/doi.org\/10.1002\/chem.200901757","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,10,13]]}}}