Grosse, Christian

[["dc.bibliographiccitation.firstpage","10049"],["dc.bibliographiccitation.issue","21"],["dc.bibliographiccitation.journal","Inorganic Chemistry"],["dc.bibliographiccitation.lastpage","10059"],["dc.bibliographiccitation.volume","48"],["dc.contributor.author","Stollenz, Michael"],["dc.contributor.author","John, Michael"],["dc.contributor.author","Gehring, Henrike"],["dc.contributor.author","Dechert, Sebastian"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Meyer, Franc"],["dc.date.accessioned","2018-11-07T11:22:18Z"],["dc.date.available","2018-11-07T11:22:18Z"],["dc.date.issued","2009"],["dc.description.abstract","The synthesis of three pyrazole-based, potentially binucleating ligands 3,5-bis(R(1)N(CH(3))CH(2))-4-R(2)pyrazole (L(1)H: R(1) pyridyl-2-methyl-, R(2) = Ph; L(2)H: R(1) = 8-quinolyl-, R(2) = H; L(3)H: R(1) = 8-quinolyl-, R(2) = Ph) is described. Reaction of L(1-3)H with 1 equiv. of mesitylcopper affords oligonuclear homoleptic complexes of the type [CuL](n) (1-3). The single crystal X-ray structure of 2 shows a tetranuclear assembly of linear coordinated copper(I)-centers bridged by pyrazolato ligands that alternate above and below the Cu(4) plane, with additional weak interactions from some of the ligand side arms. As the single crystal X-ray structure of 3 reveals, phenyl substitution at the 4-position of the pyrazolato framework leads to significant structural modification of the Cu(4) array, giving a rhombical tetranuclear complex with two linear coordinated copper(I) centers that exhibit a short intramolecular Cu:: center dot Cu contact (2.8212(10) angstrom) and two peripheral copper(I) centers in a distorted tetrahedral coordination mode. Thus, 3 represents a very rare example of an inorganic pyrazolato cuprate which can also be viewed as a partly rearranged structural isomer of 2. Furthermore, the crystal lattice of 3 shows an extended network of intra- and intermolecular pi-pi stacking interactions between the aromatic rings. In solution, 1-3 each form two types of oligomers a and b that slowly (<1 s(-1)) equilibrate at room temperature. Using Diffusion Ordered Spectroscopy (DOSY) and variable temperature (1)H NMR spectroscopy it can be shown that a and b correspond to a tetrameric and a (planar) trimeric species. Coordination of the pyridyl/quinolyl side arms that is observed in the solid state seems to be only transient in solution."],["dc.description.sponsorship","Fonds der Chernischen Industrie"],["dc.identifier.doi","10.1021/ic900727h"],["dc.identifier.isi","000270987400019"],["dc.identifier.pmid","19803532"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/55964"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Amer Chemical Soc"],["dc.relation.issn","0020-1669"],["dc.title","Oligonuclear Homoleptic Copper(I) Pyralzolates with Multinucleating Ligand Scaffolds: High Structural Diversity in Solid-State and Solution"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","3708"],["dc.bibliographiccitation.issue","14"],["dc.bibliographiccitation.journal","Organometallics"],["dc.bibliographiccitation.lastpage","3725"],["dc.bibliographiccitation.volume","30"],["dc.contributor.author","Stollenz, Michael"],["dc.contributor.author","Gehring, Henrike"],["dc.contributor.author","Konstanzer, Vera"],["dc.contributor.author","Fischer, Stefan"],["dc.contributor.author","Dechert, Sebastian"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Meyer, Franc"],["dc.date.accessioned","2018-11-07T08:54:12Z"],["dc.date.available","2018-11-07T08:54:12Z"],["dc.date.issued","2011"],["dc.description.abstract","The synthesis of a series of new pyrazole-based binucleating compartmental ligands, 3,5-bis((RRN)-R-2-N-3)-(4-R-1)-pyrazoles (LH)-H-1-(LH)-H-6 ((LH)-H-1, R-1 = H, R-2 = Me, R-3 = 2-py(CH2); (LH)-H-2, R-1 = Ph, R-2 = Me, R-3 = 2-py(CH2); (LH)-H-3, R-1 = H, R-2 = Cy, R-3 = 2-py(CH2); (LH)-H-4, R-1 = Ph, R-2 = Cy, R-3 = 2-py(CH2); (LH)-H-5, R-1 = Ph, R-2, R-3 = 2-py(CH2), L6H, R-1 = Ph, R-2 = Me, R-3 = 8-quin), together with the X-ray crystal structure of (LH)-H-3 is reported. After deprotonation and subsequent reaction with 2 equiv of [Cu-I(CH3CN)(4)](BF4) and PMe3, (LH)-H-3 forms the stable binuclear Cu-I complex [L-3{Cu(PMe3)}(2)](BF4) (1). The analogous reaction with (LH)-H-6 and 2 equiv of tert-butyl isonitrile affords [L-6{Cu(CNtBu)}(2)](BF4) (2), 1 and 2 represent the first examples of binuclear Cu-I-pyrazolate complexes of the type [LCu21]X that have been characterized by their X-ray crystal structures. With respect to the planes spanned by the pyrazolate backbone, 1 shows a cis orientation of the PMe3 ligands, whereas 2 exhibits a trans arrangement of the tBuNC ligands. (LH)-H-1-(LH)-H-6 are shown to react with 4 equiv of mesitylcopper and stoichiometric amounts of dioxygen, leading to the formation of the unusually stable organocopper frameworks 3-8. These complexes follow a general structural principle that is best described by the heteroleptic O-centered cuprate anion [(MesCu(I))(4) (mu(4)-O)](2-) linked via four trans-oriented sigma-mesityl bridges to two flanking binuclear Cu-I-pyrazolates [(L-1-L-6)Cu-2(I)](+). Thus, 1 and 2 can also be viewed as capping binuclear Cu-I-complex units that are concealed by two ancillary PMe3 and tBuNC ligands, respectively. The exemplary reaction of 4 with an excess of dimethyl acetylenedicarboxylate (DMDAC) supports the observed cuprate features of 3-8, since after hydrolysis the corresponding (syn-)addition product MesC(CO2Me)=C(CO2Me)H (9) and the free ligand (LH)-H-2 are found as major products."],["dc.description.sponsorship","Fonds der Chemischen Industrie"],["dc.identifier.doi","10.1021/om100836j"],["dc.identifier.isi","000292847900006"],["dc.identifier.purl","https://resolver.sub.uni-goettingen.de/purl?gs-1/8936"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/22617"],["dc.notes.intern","Merged from goescholar"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Amer Chemical Soc"],["dc.relation.issn","0276-7333"],["dc.rights","Goescholar"],["dc.rights.uri","https://goescholar.uni-goettingen.de/licenses"],["dc.title","From Pyrazolate-Based Binuclear Copper(I) Complexes to Octanuclear sigma-Mesityl-Bridged mu(4)-Oxo-Cuprocuprates: Controlled Dioxygen Splitting by Organocopper Scaffolds"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dc.type.version","published_version"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","123"],["dc.bibliographiccitation.issue","1"],["dc.bibliographiccitation.journal","Amino Acids"],["dc.bibliographiccitation.lastpage","124"],["dc.bibliographiccitation.volume","37"],["dc.contributor.author","Grosse, Christian"],["dc.date.accessioned","2018-11-07T08:27:53Z"],["dc.date.available","2018-11-07T08:27:53Z"],["dc.date.issued","2009"],["dc.identifier.isi","000267823800425"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/16300"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Springer"],["dc.publisher.place","Wien"],["dc.relation.issn","1438-2199"],["dc.relation.issn","0939-4451"],["dc.title","How to assemble a protein tag for purification, crystallisation and phasing"],["dc.type","conference_abstract"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.journal","Abstracts of Papers of the American Chemical Society"],["dc.bibliographiccitation.volume","242"],["dc.contributor.author","Stollenz, Michael"],["dc.contributor.author","Gehring, Henrike"],["dc.contributor.author","Konstanzer, Vera"],["dc.contributor.author","Fischer, Stefan"],["dc.contributor.author","Dechert, Sebastian"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Meyer, Franc"],["dc.date.accessioned","2018-11-07T08:53:05Z"],["dc.date.available","2018-11-07T08:53:05Z"],["dc.date.issued","2011"],["dc.identifier.isi","000299378300024"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/22326"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Amer Chemical Soc"],["dc.publisher.place","Washington"],["dc.relation.conference","242nd National Meeting of the American-Chemical-Society (ACS)"],["dc.relation.eventlocation","Denver, CO"],["dc.relation.issn","0065-7727"],["dc.title","From pyrazolate-based binuclear copper(I) complexes to octanuclear s-mesityl-bridged m(4)-oxo-cuprocuprates: A concept for small molecule activation by functional molecular scaffolds"],["dc.type","conference_abstract"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","8956"],["dc.bibliographiccitation.issue","29"],["dc.bibliographiccitation.journal","Chemistry - A European Journal"],["dc.bibliographiccitation.lastpage","8963"],["dc.bibliographiccitation.volume","14"],["dc.contributor.author","Tietze, Lutz Friedjan"],["dc.contributor.author","Spiegl, Dirk A."],["dc.contributor.author","Stecker, Florian"],["dc.contributor.author","Major, Julia"],["dc.contributor.author","Raith, Christian"],["dc.contributor.author","Grosse, Christian"],["dc.date.accessioned","2018-11-07T11:19:41Z"],["dc.date.available","2018-11-07T11:19:41Z"],["dc.date.issued","2008"],["dc.description.abstract","The stereoselective synthesis of 4-dehydroxydiversonol (4) employing enantioselective palladium-catalysed domino processes such as the domino Wacker-Heck and the domino Wacker-carbonylation reaction for the formation of the central chroman moiety is described. Thus, reaction of 8 with palladium(II) trifluoroacetate [Pd(OTFA)(2)] in the presence of carbon monoxide, methanol and the 2,2'-bis(oxazolin-2-yl)-1,1'-binaphthyl (BOXAX) ligand 17 led to 19 in 80% yield and 96% ee. Similarly, the chroman 7 was prepared using 8 and methyl acrylate (9) as starting material. Hydrogenation of the double bond, oxidation of the benzylic methylene group and intramolecular acylation of chromanone 6 provided the tetrahydroxanthenone core 5, from which the synthesis of 4 was completed. The relative configuration of 4 could be established by crystal structure analysis."],["dc.identifier.doi","10.1002/chem.200800967"],["dc.identifier.isi","000260278900028"],["dc.identifier.pmid","18698572"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/55343"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Wiley-v C H Verlag Gmbh"],["dc.relation.issn","1521-3765"],["dc.relation.issn","0947-6539"],["dc.title","Stereoselective Synthesis of 4-Dehydroxydiversonol Employing Enantioselective Palladium-Catalysed Domino Reactions"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","1744"],["dc.bibliographiccitation.issue","15"],["dc.bibliographiccitation.journal","Chemical Communications"],["dc.bibliographiccitation.lastpage","1746"],["dc.contributor.author","Stollenz, Michael"],["dc.contributor.author","Gross, Christian"],["dc.contributor.author","Meyer, Franc"],["dc.date.accessioned","2018-11-07T11:16:00Z"],["dc.date.available","2018-11-07T11:16:00Z"],["dc.date.issued","2008"],["dc.description.abstract","A new compartmental pyrazole-derived chelating ligand, four equivalents of mesitylcopper and stoichiometric amounts of di-oxygen lead to the formation of a remarkably stable organometallic framework that can be described as a heteroleptic O-centered cuprate anion [(MesCu(I))(4)(mu(4)-O)](2-) linked via sigma-mesityl-bridges to two surrounding binuclear Cu(I)-pyrazolate clamps."],["dc.identifier.doi","10.1039/b717571j"],["dc.identifier.isi","000254554800004"],["dc.identifier.pmid","18379679"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/54493"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Royal Soc Chemistry"],["dc.relation.issn","1359-7345"],["dc.title","An unusually stable octanuclear sigma-mesityl-bridged mu(4)-oxo-copper(I) complex encapsulated by a pyrazolate-based compartmental ligand scaffold"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","10428"],["dc.bibliographiccitation.issue","37"],["dc.bibliographiccitation.journal","Chemical Communications"],["dc.bibliographiccitation.lastpage","10430"],["dc.bibliographiccitation.volume","47"],["dc.contributor.author","Burger, Boris"],["dc.contributor.author","Dechert, Sebastian"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Demeshko, Serhiy"],["dc.contributor.author","Meyer, Franc"],["dc.date.accessioned","2018-11-07T09:00:57Z"],["dc.date.available","2018-11-07T09:00:57Z"],["dc.date.issued","2011"],["dc.description.abstract","A novel pyrazolate-based diiron(II) complex shows five different binding modes of exogenous carboxylate ligands in a single crystal structure. Temperature dependent X-ray data reveal thermally induced disorder due to carboxylate dynamics that resemble the carboxylate shift, as it is known from various diiron enzyme active sites."],["dc.description.sponsorship","DFG [IRTG 1422]; Evonik Foundation"],["dc.identifier.doi","10.1039/c1cc13756e"],["dc.identifier.isi","000294500600072"],["dc.identifier.pmid","21842055"],["dc.identifier.purl","https://resolver.sub.uni-goettingen.de/purl?gs-1/8677"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/24289"],["dc.notes.intern","Merged from goescholar"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Royal Soc Chemistry"],["dc.relation.issn","1364-548X"],["dc.relation.issn","1359-7345"],["dc.rights","Goescholar"],["dc.rights.uri","https://goescholar.uni-goettingen.de/licenses"],["dc.title","Visualising the carboxylate shift at a bioinspired diiron(II) site in the solid state"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dc.type.version","published_version"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","111"],["dc.bibliographiccitation.issue","2"],["dc.bibliographiccitation.journal","Journal of Biomolecular NMR"],["dc.bibliographiccitation.lastpage","119"],["dc.bibliographiccitation.volume","49"],["dc.contributor.author","Gruene, Tim"],["dc.contributor.author","Cho, Min-Kyu"],["dc.contributor.author","Karyagina, Irina"],["dc.contributor.author","Kim, Hai-Young"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Giller, Karin"],["dc.contributor.author","Zweckstetter, Markus"],["dc.contributor.author","Becker, Stefan"],["dc.date.accessioned","2018-11-07T08:59:23Z"],["dc.date.available","2018-11-07T08:59:23Z"],["dc.date.issued","2011"],["dc.description.abstract","Long-range structural information derived from paramagnetic relaxation enhancement observed in the presence of a paramagnetic nitroxide radical is highly useful for structural characterization of globular, modular and intrinsically disordered proteins, as well as protein protein and protein-DNA complexes. Here we characterized the conformation of a spin-label attached to the homodimeric protein CylR2 using a combination of X-ray crystallography, electron paramagnetic resonance (EPR) and NMR spectroscopy. Close agreement was found between the conformation of the spin label observed in the crystal structure with interspin distances measured by EPR and signal broadening in NMR spectra, suggesting that the conformation seen in the crystal structure is also preferred in solution. In contrast, conformations of the spin label observed in crystal structures of T4 lysozyme are not in agreement with the paramagnetic relaxation enhancement observed for spin-labeled CylR2 in solution. Our data demonstrate that accurate positioning of the paramagnetic center is essential for high-resolution structure determination."],["dc.description.sponsorship","Max Planck Society; Fonds der Chemischen Industrie; DFG [ZW 71/2-2, 3-2]"],["dc.identifier.doi","10.1007/s10858-011-9471-y"],["dc.identifier.isi","000288768700006"],["dc.identifier.pmid","21271275"],["dc.identifier.purl","https://resolver.sub.uni-goettingen.de/purl?gs-1/6660"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/23880"],["dc.notes.intern","Merged from goescholar"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Springer"],["dc.relation.issn","0925-2738"],["dc.rights","Goescholar"],["dc.rights.uri","https://goescholar.uni-goettingen.de/licenses"],["dc.title","Integrated analysis of the conformation of a protein-linked spin label by crystallography, EPR and NMR spectroscopy"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dc.type.version","published_version"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","651"],["dc.bibliographiccitation.issue","9"],["dc.bibliographiccitation.journal","Nature Methods"],["dc.bibliographiccitation.lastpage","U39"],["dc.bibliographiccitation.volume","6"],["dc.contributor.author","Rodriguez, Dayte D."],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Himmel, Sebastian"],["dc.contributor.author","Gonzalez, Cesar"],["dc.contributor.author","de Ilarduya, Inaki M."],["dc.contributor.author","Becker, Stefan"],["dc.contributor.author","Sheldrick, George M."],["dc.contributor.author","Usón, Isabel"],["dc.date.accessioned","2018-11-07T11:25:19Z"],["dc.date.available","2018-11-07T11:25:19Z"],["dc.date.issued","2009"],["dc.description.abstract","Ab initio macromolecular phasing has been so far limited to small proteins diffracting at atomic resolution (beyond 1.2 angstrom) unless heavy atoms are present. We describe a general ab initio phasing method for 2 angstrom data, based on combination of localizing model fragments such as small alpha-helices with Phaser and density modification with SHELXE. We implemented this approach in the program Arcimboldo to solve a 222-amino-acid structure at 1.95 angstrom."],["dc.identifier.doi","10.1038/NMETH.1365"],["dc.identifier.isi","000269382900013"],["dc.identifier.pmid","19684596"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/56594"],["dc.notes.submitter","Najko"],["dc.publisher","Nature Publishing Group"],["dc.relation.issn","1548-7091"],["dc.title","Crystallographic ab initio protein structure solution below atomic resolution"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","11820"],["dc.bibliographiccitation.issue","49"],["dc.bibliographiccitation.journal","The Journal of Physical Chemistry A"],["dc.bibliographiccitation.lastpage","11836"],["dc.bibliographiccitation.volume","119"],["dc.contributor.author","Druzhinin, Sergey I."],["dc.contributor.author","Galievsky, Victor A."],["dc.contributor.author","Demeter, Attila"],["dc.contributor.author","Kovalenko, Sergey A."],["dc.contributor.author","Senyushkina, Tamara A."],["dc.contributor.author","Dubbaka, Srinivas R."],["dc.contributor.author","Knoche, Paul"],["dc.contributor.author","Mayer, Peter"],["dc.contributor.author","Grosse, Christian"],["dc.contributor.author","Stalke, Dietmar"],["dc.contributor.author","Zachariasse, Klaas A."],["dc.date.accessioned","2018-11-07T09:47:35Z"],["dc.date.available","2018-11-07T09:47:35Z"],["dc.date.issued","2015"],["dc.description.abstract","From X-ray structure analysis, amino twist angles of 90.0 degrees for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7 degrees for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7 degrees for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4 degrees of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 degrees C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Phi'(ICT)/Phi(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments mu(e)(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 degrees C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE reversible arrow ICT reaction, with LE as the precursor, with a forward rate constant k(a) = 5.6 x 10(12) s(-1) and a back-reaction kd similar to 0.05 x 10(12) s(-1). With MMD in the strongly polar solvent MeCN, ICT is faster: k(a) = 10 x 10(12) s(-1). In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 x 10(12) s(-1). The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with k(a) = 0.24 x 10(12) s(-1). Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE -> ICT reaction of MMD as compared with DMABN (k(a) = 0.24 x 10(12) s(-1) in MeCN) is caused by a smaller energy gap Delta E(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger Delta E(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane)."],["dc.description.sponsorship","Alexander von Humboldt Foundation"],["dc.identifier.doi","10.1021/acs.jpca.5b09368"],["dc.identifier.isi","000366339400008"],["dc.identifier.pmid","26559045"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/35143"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Amer Chemical Soc"],["dc.relation.issn","1089-5639"],["dc.title","Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]