HPRC SC 2019 Joshi, H.; Kharel, S.; Ehnbom, A. ; Skopek, Hess, G. D.; - - PowerPoint PPT Presentation

HPRC SC 2019

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

MOLECULAR JUMP ROPE:

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

INTRODUCTION

▪ Molecular devices mimicking the properties of a m

• l

e c u l a r rotor where featuring a rotating and a static component is sought. ▪ Novel ''jump-rope'' process was observed in these ''parachute'' complexes while attempting to make molecular gyroscopes with a differentdesign. ▪ One potential application of these is the miniaturization of e l e c t r

• n

i c components.

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

Re P P OC CO Re P P OC CO Re P P OC X P P Re OC X

Relative Stability

X = Cl ( ) and Br ( )

– 0.4 – 0.2 – 3.4 – 3.6 + 3.8 + 2.0

OC CO CO X OC CO X CO

▪ Computing relative thermodynamic stability of byproducts in molecular devices

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

MOLECULAR JUMP ROPE:

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

SELECTED DATA

▪ Predicting reaction outcome before performing experiments.

MOLECULAR JUMP ROPE:

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

Pt P Cl Pt P Cl Cl Pt P P Cl Cl P P Pt Cl Cl

Relative Stability – 5.5 – 5.1 – 8.9 – 8.5 – 5.8 – 9.2 + 2.9 + 10.6 – 0.1 – 4.1 – 5.8 –12.7 –14.3 + 15.7 + 3.9 + 3.1 – 3.2 – 4.1 + 1.7

Pt Cl Cl

O O O O O

P

O

P P P

O O O O O

Pt Cl Cl

+ 1.5 + 2.9 + 10.6 + 7.6 + 6.8 + 5.6 + 4.9

n-13 n-13 n-13 n-13 n-13 n-13 n-13

P

n-13

Cl

n-13 n-13

P

n-13 n-13 n*-13 n*-13

O

n*-15 n*-13 n*-13 n*-13

macro- cycle size n n* g/25 22 20 f/23 20 18 e/21 18 16 d/19 16 14 c/17 14 12 b/15 12 10 a/13 10 8

not observed in experiments

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

SELECTED DATA

MOLECULAR JUMP ROPE:

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

SELECTED DATA

▪ Simulated spectroscopic data at different temperature to obtain rotational barriers.

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

▪ Experimental spectroscopic data at different temperatures.

MOLECULAR JUMP ROPE:

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

METHOD

▪A combination of molecular dynamics and electronic structure theory (DFT). ▪ HPRC resources: 28 cores (TERRA) and 20 cores (ADA), 150 h per optimization (incl. frequency calculations). ▪Solvent models and dispersion corrections were also implemented in the atomistic quantum software package Gaussian 09.

1

E DFT

2

LOCALMINIMUM

E

1

LOCALMINIMUM

2

GLOBALMINIMUM

MD Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463

MOLECULAR JUMP ROPE:

Andreas Ehnbom ( www.andreasehnbom.se )

• Dr. John A. Gladysz
• Dr. Lisa M. Pérez
• Dr. Michael B. Hall

MULTIRINGED METAL-COMPLEXES THAT REALLY KNOW HOW TO JUMP

ACKNOWLEDGEMENTS

▪ A special thanks to Dr. Lisa M. Pérez (manager of LMS, Laboratory for Molecular Simulations at TAMU) and ▪ Professor Michael B. Hall (director of LMS) (co-advisor)

Joshi, H.; Kharel, S.; Ehnbom, A.; Skopek, Hess, G. D.; Fiedler, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. J. Am. Chem. Soc. 2018, 140,8463