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Naphthalonitriles featuring efficient emission in solution and in the solid state.

ABSTRACT: In this work, a series of ?-substituted diphenylnaphthalonitriles were synthesized and characterized. They show efficient emission in solution and in the aggregated state and their environment responsiveness is based on having variable substituents at the para-position of the two phenyl moieties. The excited state properties were fully investigated in tetrahydrofuran (THF) solutions and in THF/H₂O mixtures. The size of the aggregates in aqueous media were measured by dynamic light scattering (DLS). The steady-state and time-resolved photoluminescence spectroscopy studies revealed that all the molecules show intense fluorescence both in solution and in the aggregated state. In THF solutions, a blue emission was observed for the unsubstituted (H), methyl- (Me) and tert-butyl- (t-Bu) substituted ?-diphenylnaphthalonitriles, which can be attributed to a weak ?-donor capability of these groups. On the other hand, the methoxy- (OMe), methylsulfanyl- (SMe) and dimethylamino- (NMe₂) substituted compounds exhibit a progressive red-shift in emission compared to H, Me and t-Bu due to a growing ?-electron donating capability. Interestingly, upon aggregation in water-containing media, H, Me and t-Bu show a slight red-shift of the emission and a blue-shift is observed for OMe, SMe and NMe₂. The crystal structure of Me allowed a detailed discussion of the structure-property relationship. Clearly, N-containing substituents such as NMe₂ possess more electron-donating ability than the S-based moieties such as SMe. Moreover, it was found that NMe₂ showed higher luminescence quantum yields (?_F) in comparison to SMe, indicating that N-substituted groups could enhance the fluorescence intensity. Therefore, the ?-donor nature of the substituents on the phenyl ring constitutes the main parameter that influences the photophysical properties, such as excited state lifetimes and photoluminescence quantum yields. Hence, a series of highly luminescent materials from deep blue to red emission depending on substitution and environment is reported with potential applications in sensing, bioimaging and optoelectronics.

SUBMITTER: Thulaseedharan Nair Sailaja S

PROVIDER: S-EPMC7722630 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Naphthalonitriles featuring efficient emission in solution and in the solid state.

Thulaseedharan Nair Sailaja Sidharth S Maisuls Iván I Kösters Jutta J Hepp Alexander A Faust Andreas A Voskuhl Jens J Strassert Cristian A CA

Beilstein journal of organic chemistry 20201202

In this work, a series of γ-substituted diphenylnaphthalonitriles were synthesized and characterized. They show efficient emission in solution and in the aggregated state and their environment responsiveness is based on having variable substituents at the <i>para</i>-position of the two phenyl moieties. The excited state properties were fully investigated in tetrahydrofuran (THF) solutions and in THF/H<sub>2</sub>O mixtures. The size of the aggregates in aqueous media were measured by dynamic li ...[more]

PMID: 33335604

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Project description:Several complexes of "PtL2" composition containing two cyanoxime anions - 2-oximino-2-cyano-N-piperidineacetamide (PiPCO-) and 2-oximino-2-cyano-N-morpholylacetamide (MCO-) - have been obtained and characterized both in solution and in the solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes and dark-green [PtL2]n 1D polymers, while for the MCO- anion a red, solvent containing dimeric [Pt(MCO)2·DMSO]2 complex has also been isolated. The interconversion of polymorphs was investigated. The monomeric PtL2 units are arranged into anisotropic extended solid [PtL2]n polymers with the help of PtPt metallophilic interactions. Crystal structures of monomeric PtL2 (L = PiPCO-, MCO-) and red dimeric [Pt(MCO)2·DMSO]2 complexes were determined and revealed the cis-arrangement of cyanoxime anions. The Pt-Pt distance in the "head-to-tail" red dimer was found to be 3.133 Å. The structure of the polymeric [Pt(PiPCO)2]n compound was elucidated using the EXAFS method and evidenced the formation of Pt-wires with ?3.15 Å intermetallic separation. The EPR spectra of both 1D polymers at variable temperatures indicate the absence of Pt(iii) species. Both pure dark-green [PtL2]n polymers showed a considerable room temperature electrical conductivity of 20-30 S cm-1, which evidences the formation of a mixed valence Pt(ii)/Pt(iv) system. We discovered that these 1D polymeric [PtL2]n complexes show an intense NIR fluorescence beyond 1000 nm, while yellow monomeric PtL2 complexes are not emissive at all. The room temperature excitation spectra of 1D polymeric [PtL2]n complexes demonstrated their strong emission beyond 1000 nm regardless of the used excitation wavelength between 350 and 800 nm, which is typical of systems with delocalized charge carriers. For the first time the formation of mixed valence "metal wires" held together by metallophilic interactions is directly linked both with an intense fluorescence in the NIR region of the spectrum and with the electrical conductivity. The effect of the concentration of [PtL2]n complexes dispersed in the dielectric salt matrix on the photoluminescence wavelength and intensity was investigated. Both polymers show a quantum yield that is remarkably high for this region of the spectrum, reaching ?2%. Variable temperature emission of polymeric [PtL2]n in the -190-+60 °C range was studied as well.

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Naphthalonitriles featuring efficient emission in solution and in the solid state.

Publications

Naphthalonitriles featuring efficient emission in solution and in the solid state.

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