Optical spectroscopy of exchange-coupled transition metal complexes

McCarthy, Paul J.; Güdel, Hans U.

doi:10.1016/0010-8545(88)80002-x

Cited by 128 publications

(74 citation statements)

References 187 publications

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“…The crystal field spectra of 3d n transition metal ion have been studied in detail over the last two decades [1][2][3][4]. Of the whole 3d n system, the optical properties of Mn 2+ ion have received special attention due to its half-filled shell configuration t e 2~ and numerous excellent investigations have beed made [5][6][7][8][9][10].…”

Section: -Introductionmentioning

confidence: 99%

Optical investigations of Mn2+ ion in Cs2CdCl4 and CsCaCl3 single crystals

1991

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Summary. --Polarized absorption, emission and excitation spectra of Cs2CdC14:Mn 2+ and emission as well as excitation spectra of CsCaC13:Mn 2+ single crystals at temperatures down to 77 K are reported. The general features of the spectra are fruitfully analysed within the framework of the strong fieldscheme of Tanabe and Sugano including Trees' correction. Some finer structure of the crystal field independent levels are observed which are rationalized in terms of vibrational mechanism. A detailed analysis of the spectra indicates octahedral site symmetry around the central metal ion.PACS 71.55 -Impurity and defect levels. PACS 78.50 -Impurity and defect absorption in solids. -Introduction.The crystal field spectra of 3d n transition metal ion have been studied in detail over the last two decades [1][2][3][4]. Of the whole 3d n system, the optical properties of Mn 2+ ion have received special attention due to its half-filled shell configuration t e 2~ and numerous excellent investigations have beed made [5][6][7][8][9][10]. In Mn 2+ doped 2g g/ chlorides, sharp, intense line emissions have been observed. These luminescent transitions could make these materials potential candidates for lasers and phosphors. In continuation of our previous studies on Mn 2+ ion in chloride host [5][6][7]13], we report here the optical properties of Mn 2+ doped in Cs2CdC14 and CsCaCls single crystals.

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Section: -Introductionmentioning

confidence: 99%

Optical investigations of Mn2+ ion in Cs2CdCl4 and CsCaCl3 single crystals

1991

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“…The comparison with existing spectroscopic data on isoelectronic systems shows a large variation of spectroscopic and magnetic properties and therefore considerable potential for the tuning of these properties by chemical variation of the ligand systems and oxidation states of the metal centers. The wide variety of spectroscopic observations and excited state behavior has been extensively studied for binuclear compounds of chromium(III), where a variety of absorption and luminescence techniques can be applied (8,9). Binuclear complexes of copper(I1) have been investigated in detail because of their simple dl-d' hole configuration, making them ideal model systems for experimental and theoretical studies.…”

Section: Introductionmentioning

confidence: 99%

“…Binuclear complexes of copper(I1) have been investigated in detail because of their simple dl-d' hole configuration, making them ideal model systems for experimental and theoretical studies. (8,(10)(11)(12) Other metals, such as iron(II1) and manganese(II1) in this work, have received much less attention (8). The work on…”

Section: Introductionmentioning

confidence: 99%

Single-crystal absorption spectroscopy of binuclear complexes of iron(III) and manganese(III) with the μ-oxo-bis(μ-acetato)dimetal core

Pelletier¹,

Reber

1995

Can. J. Chem.

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Single-crystal absorption spectroscopy at variable temperature is used to determine exchange couplings between transition metal centers in both the electronic ground and excited states in two new homobimetallic complexes with the formula [LM(y-O)(y-CH3C02)2ML'](C104)2, where M is iron(II1) or manganese(II1).L and L' denote 1,4,7-triazacyclononane and 1,4,7-trimethyl-l,4,7-triazacyclononane, respectively. Values for the ground state exchange coupling constant J are -295 cm-I and +I0 cm-I for the iron and manganese compounds, respectively, using He, = -JS,.S,. Exchange interactions in excited states are qualitatively analyzed, indicating that a spin-forbidden transition of the Fe-Fe binuclear unit occurs with significant intensity by the single-ion mechanism, and not as expected by the Tanabe pair intensity mechanism for spin-forbidden transitions, the dominant mechanism for isoelectronic complexes of manganese(I1).

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“…In contrast to a large number of d-block complexes with exchange coupling between paramagnetic metal centers, where quantities such as ground-state exchange splittings can be directly determined from luminescence and absorption spectra [18], no such energy differences are resolved in our spectra. This is not unexpected for lanthanide ions, as the exchange effects are much weaker than those of the d-block elements, illustrated by a large number of magnetic measurements for lanthanide complexes with nitroxide radical ligands [13,32,33].…”

Section: Phenomenological Correlations Between Optical Spectra and Mamentioning

confidence: 99%

“…Quantitative information on the optical spectroscopy and the properties of excited electronic states is essential in the search for such new materials. A recent review [3] on molecular solids incorporating free radicals indicates that their electronic spectroscopy has not been investigated in detail, in marked contrast to transition metal compounds with diamagnetic ligands, for which the effects of magnetic exchange interactions on absorption and luminescence spectra have been studied extensively over the past decades [18][19][20]. Even more recently, the room-temperature solution UV-VIS absorption and NMR spectroscopy of several d-block ions with nitroxide radical ligands has been summarized in a review [4].…”

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confidence: 98%