Pi-interaction

In chemistry, π-effects or π-interactions are a type of non-covalent interaction that involves π systems. Just like in an electrostatic interaction where a region of negative charge interacts with a positive charge, the electron-rich π system can interact with a metal (cationic or neutral), an anion, another molecule and even another π system.^[1] Non-covalent interactions involving π systems are pivotal to biological events such as protein-ligand recognition.^[2]

Types

The most common types of π-interactions involve:

Metal–π interactions: involves interaction of a metal and the face of a π system, the metal can be a cation (known as cation–π interactions) or neutral
Polar–π interactions: involves interaction of a polar molecule and quadrupole moment a π system.

Polar π interaction between water molecule and benzene

Aromatic–aromatic interactions (π stacking): involves interactions of aromatic molecules with each other.
- Arene–perfluoroarene interaction: electron-rich benzene ring interacts with electron-poor hexafluorobenzene.

π donor–acceptor interactions: interaction between low energy empty orbital (acceptor) and a high-energy filled orbital (donor).

Donor-acceptor interaction between hexamethylbenzene (donor) and tetracyanoethylene (acceptor)

Anion–π interactions: interaction of anion with π system
Cation–π interactions: interaction of a cation with a π system
C–H–π interactions: interaction of C-H with π system: These interactions are well studied using experimental as well as computational techniques.^[3]^[4]

^[5] ^[6]^[7]

Anion–π interactions

Anion and π–aromatic systems (typically electron-deficient) create an interaction that is associated with the repulsive forces of the structures. These repulsive forces involve electrostatic and anion-induced polarized interactions.^[8]^[9] This force allows for the systems to be used as receptors and channels in supramolecular chemistry for applications in the medical (synthetic membranes, ion channels) and environmental fields (e.g. sensing, removal of ions from water).^[10]

The first X-ray crystal structure that depicted anion–π interactions was reported in 2004.^[11] In addition to this being depicted in the solid state, there is also evidence that the interaction is present in solution.^[12]

π-effects in biological systems

π-effects have an important contribution to biological systems since they provide a significant amount of binding enthalpy. Neurotransmitters produce most of their biological effect by binding to the active site of a protein receptor. Xation-π interactions are important the acetylcholine (Ach) neurotransmitter.^[13]^[14] The structure of acetylcholine esterase includes 14 highly conserved aromatic residues. The trimethyl ammonium group of Ach binds to the aromatic residue of tryptophan (Trp). The indole site provides a much more intense region of negative electrostatic potential than benzene and phenol residue of Phe and Tyr.

In supramolecular assembly

$π$ systems are important building blocks in supramolecular assembly because of their versatile noncovalent interactions with various functional groups. Particularly, ${\ce {\pi - \pi}}$ , ${\ce {CH-\pi}}$ and ${\ce {\pi -cation}}$ interactions are widely used in supramolecular assembly and recognition.

${\ce {\pi-\pi}}$ concerns the direct interactions between two $π$ -systems; and ${\ce {cation-\pi}}$ interaction arises from the electrostatic interaction of a cation with the face of the $π$ -system. Unlike these two interactions, the ${\ce {CH-\pi}}$ interaction arises mainly from charge transfer between the C–H orbital and the $π$ -system.

References

^ Anslyn, E.V.; Dougherty, D.A. Modern Physical Organic Chemistry; University Science Books; Sausalito, CA, 2005 ISBN 1-891389-31-9
^ Meyer, EA; Castellano, RK; Diederich, F (2003). "Interactions with aromatic rings in chemical and biological recognition". Angewandte Chemie International Edition in English. 42 (11): 1210–50. doi:10.1002/anie.200390319. PMID 12645054.
^ K. Sundararajan; K. Sankaran; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-π Complexes of acetylene-ethylene: A matrix isolation and computational study". J. Phys. Chem. A. 106 (8): 1504. Bibcode:2002JPCA..106.1504S. doi:10.1021/jp012457g.
^ K. Sundararajan; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-π Complexes of acetylene-benzene: A matrix isolation and computational study". J. Mol. Str. (Theochem). 613 (1–3): 209–222. Bibcode:2002JMoSt.613..209S. doi:10.1016/S0022-2860(02)00180-1.
^ J. Rebek (2005). "Simultane Verkapselung: Moleküle unter sich". Angewandte Chemie. 117 (14): 2104–2115. Bibcode:2005AngCh.117.2104R. doi:10.1002/ange.200462839.
^ J. Rebek (2005). "Simultaneous Encapsulation: Molecules Held at Close Range". Angewandte Chemie International Edition. 44 (14): 2068–2078. doi:10.1002/anie.200462839. PMID 15761888.
^ S. Grimme (2004). "Accurate description of van der Waals complexes by density functional theory including empirical corrections". Journal of Computational Chemistry. 25 (12): 1463–73. doi:10.1002/jcc.20078. PMID 15224390. S2CID 6968902.
^ Schottel, Brandi L.; Chifotides, Helen T.; Dunbar, Kim R. (2008). "Anion-π interactions". Chemical Society Reviews. 37 (1): 68–83. doi:10.1039/b614208g. PMID 18197334.
^ Ballester P. "Anions and pi–Aromatic Systems. Do they interact attractively?" Recognition of Anions. Structure and Bonding Series, 129 (2008) 127-174 Berlin. Springer Verlag
^ Gamez, Patrick; Mooibroek, Tiddo J.; Teat, Simon J.; Reedijk, Jan (2007). "Anion Binding Involving π-Acidic Heteroaromatic Rings". Accounts of Chemical Research. 40 (6): 435–44. doi:10.1021/ar7000099. PMID 17439191.
^ Demeshko, Serhiy; Dechert, Sebastian; Meyer, Franc (2004). "Anion−π Interactions in a Carousel Copper(II)−Triazine Complex". Journal of the American Chemical Society. 126 (14): 4508–9. doi:10.1021/ja049458h. PMID 15070355.
^ Maeda, Hiromitsu; Osuka, Atsuhiro; Furuta, Hiroyuki (2004). "Anion Binding Properties of N-Confused Porphyrins at the Peripheral Nitrogen". Journal of Inclusion Phenomena. 49: 33–36. doi:10.1023/B:JIPH.0000031110.42096.d3. S2CID 95180509.
^ Dougherty, D. A. (1996). "Cation-pi Interactions in Chemistry and Biology: A New View of Benzene, Phe, Tyr, and Trp". Science. 271 (5246): 163–8. Bibcode:1996Sci...271..163D. doi:10.1126/science.271.5246.163. PMID 8539615. S2CID 9436105.
^ Kumpf, R.; Dougherty, D. (1993). "A mechanism for ion selectivity in potassium channels: computational studies of cation-pi interactions". Science. 261 (5129): 1708–10. Bibcode:1993Sci...261.1708K. doi:10.1126/science.8378771. PMID 8378771.

[1] Anslyn, E.V.; Dougherty, D.A. Modern Physical Organic Chemistry; University Science Books; Sausalito, CA, 2005 ISBN 1-891389-31-9

[2] Meyer, EA; Castellano, RK; Diederich, F (2003). "Interactions with aromatic rings in chemical and biological recognition". Angewandte Chemie International Edition in English. 42 (11): 1210–50. doi:10.1002/anie.200390319. PMID 12645054.

[3] K. Sundararajan; K. Sankaran; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-π Complexes of acetylene-ethylene: A matrix isolation and computational study". J. Phys. Chem. A. 106 (8): 1504. Bibcode:2002JPCA..106.1504S. doi:10.1021/jp012457g.

[4] K. Sundararajan; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-π Complexes of acetylene-benzene: A matrix isolation and computational study". J. Mol. Str. (Theochem). 613 (1–3): 209–222. Bibcode:2002JMoSt.613..209S. doi:10.1016/S0022-2860(02)00180-1.

[5] J. Rebek (2005). "Simultane Verkapselung: Moleküle unter sich". Angewandte Chemie. 117 (14): 2104–2115. Bibcode:2005AngCh.117.2104R. doi:10.1002/ange.200462839.

[6] J. Rebek (2005). "Simultaneous Encapsulation: Molecules Held at Close Range". Angewandte Chemie International Edition. 44 (14): 2068–2078. doi:10.1002/anie.200462839. PMID 15761888.

[7] S. Grimme (2004). "Accurate description of van der Waals complexes by density functional theory including empirical corrections". Journal of Computational Chemistry. 25 (12): 1463–73. doi:10.1002/jcc.20078. PMID 15224390. S2CID 6968902.

[8] Schottel, Brandi L.; Chifotides, Helen T.; Dunbar, Kim R. (2008). "Anion-π interactions". Chemical Society Reviews. 37 (1): 68–83. doi:10.1039/b614208g. PMID 18197334.

[9] Ballester P. "Anions and pi–Aromatic Systems. Do they interact attractively?" Recognition of Anions. Structure and Bonding Series, 129 (2008) 127-174 Berlin. Springer Verlag

[10] Gamez, Patrick; Mooibroek, Tiddo J.; Teat, Simon J.; Reedijk, Jan (2007). "Anion Binding Involving π-Acidic Heteroaromatic Rings". Accounts of Chemical Research. 40 (6): 435–44. doi:10.1021/ar7000099. PMID 17439191.

[11] Demeshko, Serhiy; Dechert, Sebastian; Meyer, Franc (2004). "Anion−π Interactions in a Carousel Copper(II)−Triazine Complex". Journal of the American Chemical Society. 126 (14): 4508–9. doi:10.1021/ja049458h. PMID 15070355.

[12] Maeda, Hiromitsu; Osuka, Atsuhiro; Furuta, Hiroyuki (2004). "Anion Binding Properties of N-Confused Porphyrins at the Peripheral Nitrogen". Journal of Inclusion Phenomena. 49: 33–36. doi:10.1023/B:JIPH.0000031110.42096.d3. S2CID 95180509.

[13] Dougherty, D. A. (1996). "Cation-pi Interactions in Chemistry and Biology: A New View of Benzene, Phe, Tyr, and Trp". Science. 271 (5246): 163–8. Bibcode:1996Sci...271..163D. doi:10.1126/science.271.5246.163. PMID 8539615. S2CID 9436105.

[14] Kumpf, R.; Dougherty, D. (1993). "A mechanism for ion selectivity in potassium channels: computational studies of cation-pi interactions". Science. 261 (5129): 1708–10. Bibcode:1993Sci...261.1708K. doi:10.1126/science.8378771. PMID 8378771.

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