Ligand non-innocence and strong correlation in manganese superoxide dismutase mimics
文献信息
Alexandra R. McIsaac, David A. Mazziotti
We examine the 1-electron reduction of manganese porphyrin complexes Mn(III) porphyrin and Mn(III) TDE-2-ImP5+, which have attracted recent interest due to their properties as superoxide dismutase mimics. We perform a series of electronic structure calculations using the variational 2-electron reduced density matrix (2-RDM) method with a large [30,30] active space that represents a wavefunction with 1019 variables, as well as the more traditional complete active space self-consistent field (CASSCF) method with a [14,14] active space. We show that the larger 2-RDM calculation, intractable with CASSCF, is required to capture the full effects of electron correlation in the molecule and predict the non-innocence of the porphyrin ligand during the reduction. The CASSCF method predicts single-reference systems exhibiting a metal-centered reduction, but the 2-RDM method predicts a strongly correlated system exhibiting a ligand-centered reduction. Based on these results, we find that the porphyrin ligand is reduced rather than the manganese, and suggest that the electron correlation plays a role in driving the ligand non-innocence.
相关文献
Well-defined hydrogen and organofunctional polysiloxanes with spiro-fused siloxane backbones
Takahiro Kawatsu, Keita Fuchise, Katsuhiko Takeuchi, Jun-Chul Choi, Kazuhiko Sato, Kazuhiro Matsumoto
DOI: 10.1039/D0PY01503B
Synthesis, characterization and self-assembly of linear and miktoarm star copolymers of exclusively immiscible polydienes
Ioannis Moutsios, Konstantina Tsitoni, Gkreti-Maria Manesi, Nikos Hadjichristidis
DOI: 10.1039/D1PY00258A
Heterotellurium-containing macrocycles towards degradable tellurium-functionalized polymers
Jieni Hu, Chuanhao Sun, Siqi Li, Yuan Yuan
DOI: 10.1039/D1PY00703C
Understanding and controlling the glass transition of HTPB oligomers
Eleftheria Dossi, Jacob Earnshaw, Laurence Ellison, Gabriella Rabello dos Santos, Hamish Cavaye, Douglas J. Cleaver
DOI: 10.1039/D1PY00233C
The effect of alkyl chain lengths on the red-to-near-infrared emission of boron-fused azomethine conjugated polymers and their film-state stimuli-responsivities
Shunsuke Ohtani, Natsumi Yamada, Masayuki Gon, Kazuo Tanaka, Yoshiki Chujo
DOI: 10.1039/D1PY00213A
Facile construction of noncovalent graft copolymers with triple stimuli-responsiveness for triggered drug delivery
Lei Xu, Hairong Wang, Hongrui Tian, Mingzu Zhang, Jinlin He, Peihong Ni
DOI: 10.1039/D1PY00135C
The self-assembly of single chain Janus nanoparticles from azobenzene-containing block copolymers and reversible photoinduced morphology transitions
Wei Wen
DOI: 10.1039/D1PY00223F
Novel imino- and aryl-sulfonate based photoacid generators for the cationic ring-opening polymerization of ε-caprolactone
Xabier Lopez de Pariza, Nicolas Zivic, Fernando Ruipérez, Timothy E. Long, Haritz Sardon
DOI: 10.1039/D1PY00734C
Engineering of pH-triggered nanoplatforms based on novel poly(2-methyl-2-oxazoline)-b-poly[2-(diisopropylamino)ethyl methacrylate] diblock copolymers with tunable morphologies for biomedical applications
Peter Černoch, Alessandro Jager, Zulfiya Černochová, Vladimir Sincari, Lindomar J. C. Albuquerque, Rafal Konefal, Ewa Pavlova, Fernando C. Giacomelli, Eliezer Jager
DOI: 10.1039/D1PY00141H
您可能还喜欢
6-氯-2H-1,4-苯并噁嗪-3(4H)-酮(CAS号:7652-29-1)应用于哪些行业?
6-氯-2H-1,4-苯并噁嗪-3(4H)-酮主要应用于医药、农药和聚合物等领域。在医药领域,该化合物可用于合成抗菌药物;在农药领域,可用作杀虫剂的中间体;在聚...
活性氧化铝(CAS号:1302-74-5)应用于哪些行业?
活性氧化铝广泛应用于医药、聚合物、传感器、半导体和催化等领域。在医药行业,活性氧化铝用作吸附剂和干燥剂,有助于去除杂质和水分。在聚合物行业,它用作增白剂和抗结块...
什么是硅胶(CAS号:112926-00-8)?
硅胶(Silica gel, pptd.,cryst.-free)是一种无定形、多孔的硅酸盐材料,主要成分为二氧化硅(SiO₂)。其结构由硅氧四面体构成,通过酸...
二乙基甲基一氢硅烷(CAS号:760-32-7)的主要用途是什么?
二乙基甲基一氢硅烷主要用于有机合成、表面处理以及作为溶剂。它还被用作合成其他硅烷化合物的原料,以及在涂料、粘合剂和密封剂中的应用。
在合成中是否有N-花生四烯酰基甘氨酸(CAS号:179113-91-8)的替代品?
在合成过程中,可以考虑使用类似结构的化合物作为替代品,例如N-亚油酰基甘氨酸或N-花生二烯酰基甘氨酸。这些替代品在结构上有类似的双键位置,但可能具有不同的物理化...
在合成中是否有1-(4-甲氧基苯基)丙烷-1,2-二酮(CAS号:10557-27-4)的替代品?
在合成过程中,可以考虑使用类似结构的化合物作为替代品,例如1-(3-甲氧基苯基)丙烷-1,2-二酮或1-(4-羟基苯基)丙烷-1,2-二酮。这些替代品具有相似的...
N-(4-氨基-1-苄基-3-羟基-5-苯基戊基)-3-甲基-2-(2-氧代四氢嘧啶-1-基)-丁酰胺 5-氧代吡咯烷-2-甲酸(CAS号:192726-06-0)通常如何合成?
该化合物通常通过一系列复杂的有机合成步骤获得。首先,通过芳香族化合物的羟基化反应获得羟基化产物,然后通过酰化反应形成酰胺中间体,最后通过环化反应得到目标产物。常...
(S)-2-氨基-3-喹啉-2-丙酸(CAS号:161513-46-8)的市场或研究趋势如何?
该化合物作为生物活性化合物,尤其是在药物化学领域表现出色。近年来,随着对新型抗炎、抗病毒和抗癌药物的研究增加,其市场和研究趋势持续增长。此外,其在神经科学领域的...
核黄素磷酸钠(CAS号:130-40-5)安全吗?
核黄素磷酸钠在常规使用条件下安全,但高剂量可能引起刺激性反应。操作时需佩戴防护手套和护目镜,避免吸入粉尘。若接触皮肤或眼睛,应立即用大量清水冲洗。急救时需根据接...
盐酸丙胺卡因杂质A(EP) 标准品(CAS号:19281-31-3)通常如何合成?
盐酸丙胺卡因杂质A(EP) 标准品可通过重氮化反应和随后的酰胺化反应合成。首先,利用氯化反应将苯环上的氢原子转化为氯原子,然后通过芳香族重氮化反应引入氨基,最后...
来源期刊
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.














![[4-(Heptyloxy)phenyl]boronic acid structure [4-(Heptyloxy)phenyl]boronic acid structure](https://cnstatic.chemtradehub.com/structs/136/136370-19-9-ad33.webp)