- Spiroconjugated Tetraaminospirenes as Donors in Color-Tunable Charge-Transfer Emitters with Donor-Acceptor Structure
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Charge-transfer emitters are attractive due to their color tunability and potentially high photoluminescence quantum yields (PLQYs). We herein present tetraaminospirenes as donor moieties, which, in combination with a variety of acceptors, furnished 12 charge-transfer emitters with a range of emission colors and PLQYs of up to 99 %. The spatial separation of their frontier molecular orbitals was obtained through careful structural design, and two DA structures were confirmed by X-ray crystallography. A range of photophysical measurements supported by DFT calculations shed light on the optoelectronic properties of this new family of spiro-NN-donor-acceptor dyes.
- Adachi, Chihaya,Adler, Florin,Chan, Chin-Yiu,Esser, Birgit,Grenz, David C.,Hermann, Mathias,Rose, Daniel,W?ssner, Jan S.,Wilbuer, Jennifer
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supporting information
(2021/12/22)
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- Poly(1,1-bis(dialkylamino)propan-1,3-diyl)s; Conformationally-controlled oligomers bearing electroactive groups
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The design of polymers with repeating [C(NR2)2CH 2CH2] units which may simultaneously provide conformational control and contain repeating electroactive centres is discussed; (NR2)2 groups would be ideally provided by ortho-phenylenediamine derivatives, with 1,8-diaminonaphthalenes as alternatives. Oligomers containing 1,8-bis(methylamino)naphthalenes, up to the hexamer, were obtained by condensation of oligomers of CH3[COCH 2CH2]nCOCH3 with 1,8-bis(methylamino)naphthalene, but attempts to prepare related oligomers from 1,2-bis(alkylamino)benzenes were unsuccessful, as only terminal ketone groups could be converted to aminals. Evidence for a strong preference for all-anti conformations of the main chain in the naphthalenediamine oligomers is provided by ring current effects on 1H NMR shifts, and by X-ray structures, which also provide evidence of intercalation in the solid state. Electrochemical studies of these oligomers show irreversible oxidation of oligomers in solution, but oxidation of longer oligomers leads to the deposition of a reddish-pink insoluble material which shows two reversible oxidation waves. Possible interpretation of these results is discussed. The Royal Society of Chemistry 2009.
- Alder, Roger W.,Hyland, Niall P.,Jeffery, John C.,Riis-Johannessen, Thomas,Riley, D. Jason
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experimental part
p. 2704 - 2715
(2009/09/07)
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- peri-Naphthylenediamines 31.* Study of interconversions of 2,3-dihydroperimidines and 1,8-bis(dialkylamino)naphthaienes. Convenient synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidine and a monoisopropyl analog of the "proton sponge"
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Efficient procedures were developed for the two-step synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidines and for the one-step synthesis of 1,3-dimethyl-2,3-dihydroperimidines starting from 1,8-diaminonaphthalenes. New possibilities of the use of 2,3-dihydroperimidinium salts in the synthesis of 1,8-bis(dialkylamino)naphthalenes ("proton sponges") containing the N-isopropyl group along with the N-methyl groups were demonstrated. The 1,1,2,2,3-pentamethyl-2,3-dihydroperimidinium cation exists in the acyclic iminium form responsible for its high reactivity.
- Ozeryanskii,Filatova,Sorokin,Pozharskii
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p. 846 - 853
(2007/10/03)
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- Synthesis, structure, and stereodynamics of an N,N-chiral 'proton sponge'
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1,8-Bis(N-benzyl-N-methylamino)naphthalene (2) and its hydrogen iodide salt [2H]+[I]- were synthesised from 1,8-diaminonaphthalene. The thermodynamic diastereomer ratios of (2) and [2H]+ in [D7]DMF are 73.4:26.6 and 89.7:10.3 respectively at 293 K. The solid state structures of the major dl-(R(N)R(N)/S(N)S(N)) diastereomers were determined by single crystal X-ray diffraction. The minor diastereomers were shown to be the meso-(R(N)S(N)) forms by performing 1H-NMR NOE studies on isotopically desymmetrized 1-(N- benzyl-N-[13C]-methylamino)-8-(N'-benzyl-N'-methylamino)naphthalene [13C]-2 and the salt [13C]-[2H]+. In [D7]DMF at 298 K, the meso form of the free base 2 is 0.6 (± 0.07) kcal · mol-1 less stable than the d1 form (ΔH°= -0.64 (±0.03) kcal · mol-1; ΔS°= -0.18 (±0.13) cal · K- 1mol-1) and the activation barriers for interconversion are ca. 14,2 (±0.4) and 14,8 (±0.4) kcal · mol-1 respectively. The effect of solvent polarity on the entropy and enthalpy change on approach to the transition state was studied. An approximate correlation with the solvent dielectric constant was found for both ΔH((+)) and ΔS((+)) and this may be ascribed to the development of a net dipole in the transition state due to substantially different hybridisation and geometry at the two nitrogen centres.
- Charmant, Jonathan P. H.,Lloyd-Jones, Guy C.,Peakman, Torren M.,Woodward, Robert L.
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p. 2501 - 2510
(2007/10/03)
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- Synthesis of a protonated C2-symmetric N,N-chiral 'proton sponge'
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The hydrogen iodide salt of 1,8-bis-(N-benzyl-N-methylamino)naphthalene was synthesised as an 89 / 11 ratio of diastereomers in good yield. The structure of the major (±)-(R(N)R(N)/S(N)S(N)) diastereomer was determined by single crystal X-ray diffraction. The minor diastereomer is shown to be the meso-(R(N)S(N)) form by performing 1H NMR n.O.e studies on isotopically desymmetrized 1-(N-benzyl-N-[13C]-methylamino)-8-(N'-benzyl-N'- methylamino)naphthalene (HI salt). The half-life of interconversion of meso and dl forms is less than 2 minutes in CD2Cl2 at ambient temperature.
- Charmant, Jonathan P. H.,Lloyd-Jones, Guy C.,Peakman, Torren M.,Woodward, Robert L.
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p. 4733 - 4736
(2007/10/03)
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- Optical properties of spiroconjugated charge-transfer dyes
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A new type of intramolecular charge-transfer dye has been prepared. The LUMO of the acceptor part (1,3-indandione) in these compounds is spiroconjugated with the HOMO of the donor part (aromatic diamine or amino thiol). The interaction between the donor and acceptor is controlled by the energy and symmetry of the frontier orbitals. The ground state dipole moments of these compounds are aligned along the long molecular axes. In the solid state, distortions of structures are observed that are consistent with partial electron shift from the donor to the acceptor. Much more pronounced electron density shifts accompany the electronic transition that is observed in the visible region of the spectrum. These transitions are of the charge-transfer (CT) type, as shown by solvatochromic and electrooptical studies. The excited state dipole moments are in the direction opposite to that of the ground state. These observations are consistent with the excited state having radical ion pair character. The new dyes are modeled using a simple Mulliken charge-transfer theory. The mixing coefficient of neutral and ionic wave functions describing these systems is used as a measure of spiroconjugation between the subchromophores. The electrooptical data provide an estimate of the contribution of the CT transitions to the hyperpolarizabilities (β) within the two-state model. The measured values of β indicate, however, that spiro dyes have two opposing contributions to their hyperpolarizabilities, one from the CT transition and one due to the acceptor subchromophore.
- Maslak, Przemyslaw,Chopra, Anu,Moylan, Christopher R.,Wortmann, Rüdiger,Lebus, Sonja,Rheingold, Arnold L.,Yap, Glenn P. A.
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p. 1471 - 1481
(2007/10/03)
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- Arylazo and poly(arylazo) dyes having at least one core radical selected from naphthyl or anthracyl and having at least one 2,3-dihydro-1,3-dialkyl perimidine substituent
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Arylazo and poly(arylazo) dyes having at least one core radical selected from naphthyl or anthracyl and having at least one 2,3-dihydro-1,3-dialkyl perimidine substituent, a guest-host composition comprising a liquid crystal host solvent and the arylazo or poly(arylazo) dichroic dye, and a liquid crystal display comprising the guest-host composition, are disclosed.
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- PERI-NAPHTHYLENEDIAMINES XII. ELIMINATION OF THE μ-CARBONYL GROUP IN 1,3-DIALKYLPERIMIDONES AND IMIDAZOLONES. A CONVENIENT METHOD FOR THE SYNTHESIS OF N,N'-DIALKYL DERIVATIVES OF PERI- AND ORTHO-DIAMINES
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N,N'-Dialkyl-substituted 1,8-diamino- and 1,2-diaminonaphthalenes are formed with good yields when the 1,3-dialkyl derivatives of perimidone and naphthoimidazolone are fused with anhydrous powdered alkali at 200-220 deg C.Sodium amide in dimethylaniline can be used instead of the alkali.
- Konstantinchenko, A. A.,Pozharskii, A. A,,Stepanova, V. N.
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p. 1195 - 1199
(2007/10/02)
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- Process for preparing 2,3-dihydro-1,3-dialkyl-2,3-dialkyl perimidines and N,N-'-dialkyl-1,8-naphthalene diamines
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Processes for preparing 2,3-dihydro-1,3-dialkyl-2,2-dialkyl perimidines and N,N'-dialkyl-1,8-naphthalene diamines are disclosed. The 2,3-dihydro-1,3-dialkyl-2,2-dialkyl perimidines are prepared by alkylating 2,3-dihydro-2,2-dialkyl perimidines with an alkylating agent in a water miscible organic solvent at room temperature to 80° C. in the presence of water and an inorganic base. N,N'-dialkyl-1,8-naphthalene diamines are prepared by hydrolyzing the 2,3-dihydro-1,3-dialkyl-2,2-dialkyl perimidines with strong aqueous acid in an aqueous organic solvent and removing a ketone by-product and the aqueous organic solvent by codistillation.
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- Liquid crystal coupled dichroic dyes
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Modifiers for pleochroic, and in particular dichroic, dyes in which a linking group contains a spacing chain of at least four linearly linked atoms that is coupled at one end to a liquid crystal moiety and is connectable at the other end to a nonionic dye chromophore to a nonionic dye to form a modified dichroic dye, to such modified dye compounds, and to their use in guest-host compositions and devices containing the dye compounds, are disclosed.
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- Preparation of a Range of NNN'N'-Tetrasubstituted 1,8-Diaminonaphthalenes
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Alkylation of 1,8-bis(methylamino)naphthalene with difunctional reagents leads to a series of 1,5-dimethylnaphtho-1,5-diazacycloalkanes (1)-(5), to 1,5-dimethylbenzonaphtho-1,5-diazacyclononane (6), and to 1,5-dimethylnaphtho-1,5-diaza-8-oxacyclodecane (7).A variety of attempts to develop a selective preparation of 1,8-bis(methylamino)naphthalene was reported.The preparation of 9,9-dimethylnaphtho-1,5-diazabicyclononane (8), naphtho-1,5-diazabicyclononane (9), and naphtho-1,5-diazabicycloundecane (10) from 1,8-diaminonaphthalene are described.Reaction of appropriate 1,4- and 1,5-dihalides with 1,8-diaminonaphthalene leads to 1,8-bis-(1-pyrrolidinyl)naphthalene (11), 1,8-bis(1,3-dihydroisoindol-2-yl)naphthalene (12), 1,8-bis-(1-piperidinyl)naphthalene (13), and 1,8-dimorpholinonaphthalene (14).Nitration of 2,7-dimethylnaphthalene gives a mixture from which 2,7-dimethyl-1,8-dinitronaphthalene may be isolated; this is reduced and alkylated to give 1,8-bis(dimethylamino)-2,7-dimethylnaphthalene (15). 1,8-Bis(dimethylamino)-2,7-dimethoxynaphthalene (16) and 1,8-bis(diethylamino)-2,7-dimethoxynaphthalene (17) are similarly prepared by reduction and alkylation of 1,8-dinitro-2,7-dimethoxynaphthalene.Reaction of 2,2-dimethyl-1,3-dihydroperimidine with αα'-dibromo-o-xylene led, surprisingly, to (12) and 5-(2-propyl)benzonaphtho-1,5-diazabicyclononane (24).
- Alder, Roger W.,Bryce, Martin R.,Goode, Nigel C.,Miller, Nigel,Owen, Judith
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p. 2840 - 2847
(2007/10/02)
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- PERI-NAPHTHYLENEDIAMINES. 1. ?-DONOR CHARACTERISTICS OF 1,8-NAPHTHYLENEDIAMINES AND 2,3-DIHYDROPERIMIDINES
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The ionization constants,IR and UV spectra, ionization potentials, and the tendency to form ? complexes with 1,3,5-trinitrobenzene were investigated in the series of N-methylated 1,8-naphthylenediamines and 2,3-dihydroperimidines.In spite of the distortion of the planar structure in 1,8-bis(dimethylamino)naphthalene, the conjugation of the dimethylamino groups with the naphthalene ring is extremely significant.The synthesis of 1-amino-8-methylaminonaphthalene and 1-amino-8-dimethylaminonaphthalene is described.
- Pozharskii, A. F.,Suslov, A. N.,Starshikov, N. M.,Popova, L. L.,Klyuev, N. A.,Adanin, V. A.
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p. 1890 - 1901
(2007/10/02)
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