N-confused porphyrin tautomers: lessons from density functional theory
文献情報
Gabriel Marchand, Hélène Roy, David Mendive-Tapia
Using first-principle calculations, we characterize the properties of N-confused porphyrins (NCP), with a focus on the differences between the 2H and 3H tautomers. We find that NCP-3H is almost as strongly aromatic as porphyrin, and about twice as aromatic, i.e., remarkably more stable, than NCP-2H, due to the less efficient π-conjugation in the latter form. The deprotonation of the NH-group at the external side of the inverted ring of NCP-2H, adds a lone pair to the π-system, which restores a strong aromaticity, while methylation has no significant effect. Investigating the impact of solvation using a continuum model, we find quite stable solvation energies with a relative dielectric constant, εr, in the 5–40 range, for both tautomers. NCP-3H presents a slightly lower energy than its NCP-2H counterpart in all solvents. However, the energy differences between the two species are of the order of the error margin of the method, hence too small to discuss the experimentally observed stabilization of NCP-3H in dichloromethane (DCM, a poorly polar solvent) and NCP-2H in N,N-dimethylformamide (DMF, a strongly polar solvent) or to extract the population ratios between the two forms in the different solvents. Therefore, the vibronic absorption spectra are also investigated in an effort to rationalize the complex absorption profiles of these NCP derivatives. We find very distinct spectra for the 2H and 3H forms in DMF and DCM, respectively, each fairly reproducing the experiment. We also find that, in the same solvent, the two species exhibit very different signatures, which allows us to conclude that the 2H and 3H tautomers are largely dominant in DMF and DCM, respectively. Interestingly, the vibrational motions that strongly participate in the shoulder of the Soret band and the multiple maxima of the Q-bands largely differ in the two tautomers.
関連文献
Super electron donor-mediated reductive transformation of nitrobenzenes: a novel strategy to synthesize azobenzenes and phenazines
Kanako Nozawa-Kumada, Erina Abe, Shungo Ito, Masanori Shigeno, Yoshinori Kondo
DOI: 10.1039/C8OB00271A
Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
Mengmeng Jia, Heng Zhang, Yongjia Lin, Dimei Chen, Yanmei Chen
DOI: 10.1039/C8OB00490K
Thiophene fused indenocorannulenes: synthesis, variable emission, and exceptional chiral configurational stability
Xiaoqi Tian, Suchaya Chaiworn, Jun Xu, Nicolas Vanthuyne, Kim K. Baldridge, Jay S. Siegel
DOI: 10.1039/D1QO00596K
Darzens reaction of thioisatins and sulfonium salts: approach to the synthesis of thiochromenone derivatives with anticancer potency
Jinhui Shen, Yang Yang, Xiaoli Hou, Wenlei Zeng, Aimin Yu, Xiaowei Zhao, Xiangtai Meng
DOI: 10.1039/C8OB00402A
Cross dehydrogenative coupling of sugar enol ethers with terminal alkenes in the synthesis of pseudo-disaccharides, chiral oxadecalins and a conjugated triene
DOI: 10.1039/C8OB00168E
Visible-light-induced iodine-anion-catalyzed decarboxylative/deaminative C–H alkylation of enamides
Jia-Xin Wang, Ya-Ting Wang, Hao Zhang, Ming-Chen Fu
DOI: 10.1039/D1QO00660F
A practical route to 2-iodoanilines via the transition-metal-free and base-free decarboxylative iodination of anthranilic acids under oxygen
DOI: 10.1039/D1QO00461A
Carbon chain shape selectivity by the mouse olfactory receptor OR-I7
Jianghai Ho, Jason Karl Liu, Radhanath Purakait, Uriel N. Morzan, Lucky Ahmed, Victor S. Batista, Hiroaki Matsunami
DOI: 10.1039/C8OB00205C
Dual-stimuli pseudorotaxane switches under kinetic control‡
Marius Gaedke, Henrik Hupatz, Hendrik V. Schröder, Simon Suhr, Kurt F. Hoffmann, Arto Valkonen, Biprajit Sarkar, Sebastian Riedel, Kari Rissanen, Christoph A. Schalley
DOI: 10.1039/D1QO00503K
こちらもおすすめ
2-メトキシ-4-(メチルスルフィニル)アミンの主な用途は何ですか?
2-メトキシ-4-(メチルスルフィニル)アミンは、主に医薬品および農薬の製造に使用されます。また、合成化学の一部として研究用材料としても利用されます。
4,6-二氯-N-甲基ピラミジンアミンの代替品はありますか?
代替品としては、4,6-二クロロピラミジンアミンや他のピラミジン系化合物が考えられます。ただし、目的と用途によって最適な代替品は異なります。
6-氯-4-甲基-1H-吲哚を含む廃棄物はどのように処理すべきですか?
6-氯-4-甲基-1H-吲哚の廃棄物は、適切な容器に収集し、密閉して保管します。温度は常温、湿度は低く、直射日光を避けて保管することを推奨します。廃棄処理は専門...
2-フローユロ-4-(トリフルオロメチル)ベンゾイドについて「に適用される法規ガイドラインは何ですか」
2-フローユロ-4-(トリフルオロメチル)ベンゾイドのCAS番号は207974-08-1です。この化合物はGHS分類で毒性物質と有害な反応物質として分類されます...
4-ニトロフェニルN-[(ベンゼルオキシルカーボンイル]グリシングリシングリシン酸はどのように保存すればよいですか?
4-ニトロフェニルN-[(ベンゼルオキシルカーボンイル]グリシングリシングリシン酸は、室温で暗所に保管し、乾燥した環境で保存することを推奨します。容器は密閉性の...
イソデスロラタドリンの代替品はありますか?
イソデスロラタドリンの代替品としては、デスロラタドリンや他の抗ヒスタミン薬が挙げられます。具体的には、デスロラタドリン、ラセカミド、フェルタドリンなどが、症状や...
5-甲氧基-1,2,3,4-四氢异喹啉盐酸盐はどのように合成されますか?
5-甲氧基-1,2,3,4-四氢异喹啉盐酸盐の一般的な合成方法は、メタノール中で5-メトキシ-1,2,3,4-四ヒュドロイソキシンを塩酸で塩化します。この反応で...
4-アミノ-5-メトキシ-2-トルエンサルホニック酸についての法規ガイドラインは何ですか?
CAS番号6471-78-9の4-アミノ-5-メトキシ-2-トルエンサルホニック酸は、GHS分類では corrosive(腐食性)と識別されます。EUのREAC...
甲基孕酮を取り扱う際の実験室安全事項は何ですか?
甲基孕酮の取り扱いは、PPE(個人保護具)の使用が必要な重要な安全事項を伴います。防塵マスク、ゴーグル、手袋を着用することが推奨されます。ドラフトチャンバーを使...
掲載誌
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











![1,2-Diphenyl-4-[2-(phenylsulfinyl)ethyl]-3,5-pyrazolidinedione structure 1,2-Diphenyl-4-[2-(phenylsulfinyl)ethyl]-3,5-pyrazolidinedione structure](https://static.chemtradehub.com/structs/57-/57-96-5-efcc.webp)
![[4-Amino-2-(methylsulfanyl)-5-pyrimidinyl]methanol structure [4-Amino-2-(methylsulfanyl)-5-pyrimidinyl]methanol structure](https://static.chemtradehub.com/structs/588/588-36-3-fc73.webp)

