THE ROLE OF CRYSTALLINE ENVIRONMENT IN THE INTRAMOLECULAR REACTIONS Elena V. Boldyreva REC-008 MDEST...

THE ROLE OF CRYSTALLINE ENVIRONMENT IN THE

INTRAMOLECULAR REACTIONS

Elena V. Boldyreva

REC-008 MDEST

Novosibirsk State University & Institute of Solid State Chemistry RAS

boldyrev@nsu.ru

Introduction

Effects of the environment Response of the environment

Conclusions

Introduction

Effects of the environment Response of the environment

Conclusions

Supramolecular systems

Supermolecules Supramolecular assemblies

Associates(dimers)

Very large molecules(proteins, DNA, RNA) solutions crystals

Supermolecules(Multisubunit proteins,

nucleoproteids)

Associates of supermolecules

Supramolecular assemblies of supermolecules (protein crystals)

Supramolecular systems

Supermolecules Supramolecular assemblies

Associates(dimers)

Very large molecules(proteins, DNA, RNA) solutions crystals

Supermolecules(Multisubunit proteins,

nucleoproteids)

Associates of supermolecules

Supramolecular assemblies of supermolecules (protein crystals)

Molecular / ionic-molecular crystals

• Van der Waals interactions

• Hydrogen bonds

• Other specific interactions

on the structures of assemblies

on the properties of assemblies

supramolecular synthesis crystal engineering statistical analyses of databases prediction of crystal structures

physical properties

chemical reactivity

important for practice intermolecular potentials

response to external actions

The effect of intermolecular interactions

molecular crystal kinetics reaction selectivity

effects of

reaction type

structures of product

temperaturewavelengthpressure

(homogeneous/heterogeneous, single-crystal single-crystal) cooperative effects

on the structures of assemblies

on the properties of assemblies

supramolecular synthesis crystal engineering statistical analyses of databases prediction of crystal structures

physical properties

chemical reactivity

important for practice intermolecular potentials

response to external actions

The effect of intermolecular interactions

molecular crystal kinetics reaction selectivity

effects of

reaction type

structures of product

temperaturewavelengthpressure

(homogeneous/heterogeneous, single-crystal single-crystal) cooperative effects

on the structures of assemblies

on the properties of assemblies

supramolecular synthesis crystal engineering statistical analyses of databases prediction of crystal structures

physical properties

chemical reactivity

important for practice intermolecular potentials

response to external actions

The effect of intermolecular interactions

molecular crystal kinetics reaction selectivity

effects of

reaction type

structures of product

temperaturewavelengthpressure

(homogeneous/heterogeneous, single-crystal single-crystal) cooperative effects

on the structures of assemblies

on the properties of assemblies

supramolecular synthesis crystal engineering statistical analyses of databases prediction of crystal structures

physical properties

chemical reactivity

important for practice intermolecular potentials

response to external actions

The effect of intermolecular interactions

molecular crystal kinetics reaction selectivity

effects of

reaction type

structures of product

temperaturewavelengthpressure

(homogeneous/heterogeneous, single-crystal single-crystal) cooperative effects

on the structures of assemblies

on the properties of assemblies

supramolecular synthesis crystal engineering statistical analyses of databases prediction of crystal structures

physical properties

chemical reactivity

important for practice intermolecular potentials

response to external actions

The effect of intermolecular interactions

molecular crystal kinetics reaction selectivity

effects of

reaction type

structures of product

temperaturewavelengthpressure

(homogeneous/heterogeneous, single-crystal single-crystal) cooperative effects

Effects of environment

• Steric restrictions• Interactions in the

second coordination sphere

• Cooperative phenomena

• Passive reaction cavity• Active reaction cavity• Flexible reaction

cavity • Feed-back phenomena

n'

n

Two groups of problems:

• Effect of the environment on the reaction rate and the very possibility of the reaction

• Response of the environment to the reaction

Introduction

Effects of the environment Response of the environment

Conclusions

Variation of the environment

• Various outersphere anions

• Different polymorphs

• Continuous distortion of the structure (variable pressure / elastic deformation)

PowderCell 2 .0

[Co(NH3)5NO2]Cl2

[Co(NH3)5NO2]Cl(NO3)

a

(a’) c0

(a’)

[Co(NH3)5NO2]I2, Pnma

[Co(NH3)5NO2]I2, C2/m

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

Linkage isomerization in [Co(NH3)5NCS]Cl2

Solution: intramolecular; crystal: intermolecular

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

[Co(NH3)5ONO]An [Co(NH3)5NO2]An

An = 2Cl-, 2Br-, 2I-, 2F-, Cl-(NO3)-, 2(NO3)-, (SO4)2-, etc. 100% linkage isomerization

<->

h

T

Linkage isomerization in [Co(NH3)5NO2]An (intramolecular)

Solution:

Crystals:

An = (C2O4)2- no photoisomerization, 100% red-ox decomposition

An = (SiF6 )2- photoisomerization not complete (40%), no red-ox decomposition

75% red-ox decomposition + 25% linkage isomerization

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

Different outersphere species

Racemization of (+)-[Co(en)3]X3

0 50 100 150 200 t, h0.0

0.2

0.4

0.6

Cl-

SCN-

Br-

I-

Linkage isomerization in [Co(NH3)5ONO]An

0 1 2 3 4 5 6 7 80

20

40

60

80

100 1

32

4

% O

NO

t, ч.

0 10000 20000 30000 400000,0

0,2

0,4

0,6

0,8

1,0

4

5

32

1

A(t

)/A

(0)

t, сек

«Free space» around the nitro-ligandin [Co(NH3)5NO2]XY

XY = 2Cl- XY = 2Br- XY = Cl-(NO3)-

XY = 2I- XY = (SiF6)2- XY = (C2O4)2-

Different polymorphs

0 2000 4000 6000 8000 10000 12000 140000

1

2

3

4

5

6

2

1

-ln

(1-

)

t, сек

0 5000 10000 150000

1

2

3

4

5

6

2

1

-ln

(1-

)

t, сек

0 5000 10000 150000

1

2

3

4

5

6

3

2

1

-ln(1

-)

t, сек

[Co(NH3)5ONO]Cl2

[Co(NH3)5ONO]Br2

[Co(NH3)5ONO]I2

Isomerization in the different polymorphs

12

1

2

1

3

2

Continuous distortionof the same structure(hydrostatic pressure)

Effect of hydrostatic pressure on the linkage isomerization

[Co(NH3)5ONO]Br2 [Co(NH3)5NO2]Br2k1

k2

V > 0 (!)

but

V# < 0

Pressure accelerates

the reaction (!)

Effect of hydrostatic pressure on the linkage isomerization

[Co(NH3)5ONO]Br2 [Co(NH3)5NO2]Br2k1

k2

V > 0 (!)

but

V# < 0

Pressure accelerates

the reaction (!)

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal single crystal / Fragmentation of crystals

Linkage isomerization in [Co(NH3)5NO2]Cl(NO3)

Continuous distortionof the same structure

(elastic bending)

Variation of the environment

holder

crystal

mirror

load laser

scale

light

121086420

700

600

500

400

300

200

100

0

21Zm

Z=wt

t, min

0.30.20.10.0

0.9

0.8

0.7

0.6W

/W0

L/L,%

FR

AC

TU

RE

Effect of elastic bending on the linkage isomerization

[Co(NH3)5NO2]Cl(NO3) [Co(NH3)5ONO]Cl(NO3)

V < 0 (!)

but

V# > 0

Quantum yielddecreases (!) in the

elastically compressed parts of the crystals

h

Effect of elastic bending on the linkage isomerization

[Co(NH3)5NO2]Cl(NO3) [Co(NH3)5ONO]Cl(NO3)

V < 0 (!)

but

V# > 0

Quantum yielddecreases (!) in the

elastically compressed parts of the crystals

h

Introduction

Effects of the environment Response of the environment

Conclusions

Effects of the environment:

• Changes in the mechanism

• Different reaction products (or no reaction at all in particular environments)

• Kinetics

• Spatial propagation (homogeneous / heterogeneous)

• Single crystal -> single crystal / Fragmentation of crystals

Response of the environment:

Changes in the mechanism

Different reaction products (or no reaction at all in particular environments)

Kinetics

Spatial propagation (homogeneous / heterogeneous)

Single crystal single crystal / Fragmentation of crystals

Response:

Macroscopic level

• Bending• Fragmentation

Microscopic level

• Changes in the interatomic distances

• Shifts in the

vibrational spectra

Lattice strain

Response:

Macroscopic level

• Bending• Fragmentation

Microscopic level

• Changes in the interatomic distances

• Shifts in the

vibrational spectra

Lattice strain

Linear strain induced by [Co(NH3)5NO2]XY [Co(NH3)5ONO]XY linkage isomerization

XY

2Cl- 2Br- 2I- (в Pnma) Cl-(NO3)- 2(NO3)

-

a/a(%) +0.13(4) +0.94(7) 0.0 -2.34(5) -1.47(8)

b/b(%) +2.0(1) +1.37(5) -1.2(1) -1.8(1) -1.47(8)

c/c(%) -3.42(5) -3.47(5) -0.92(8) +3.51(7) +2.56(5)

( ) -4.78(2) -4.52(3) - - -

V/V(%) -0.95(6) -0.84(6) -2.1(2) -0.7(1) -0.4(1)

l1/l1(%) +3.01(2) +3.38(4) 0.0 +3.51(7) +2.56(5)

l2/l2(%) +1.99(2) +1.37(2) -0.92(8) -1.8(1) -1.47(8)

l3/l3(%) -5.96(2) -5.59(3) -1.2(1) -2.34(5) -1.47(8)

Lattice strain in [Co(NH3)5NO2]Cl(NO3)

Hydrostaticpressure

Nitro - nitrito linkagephotoisomerization

Linear strain in directions of atom-atom contacts in the structure of [Co(NH3)5NO2]Cl(NO3)

Nitro - nitrito linkagephotoisomerization

Hydrostaticpressure

Effect of elastic bending on the linkage isomerization

[Co(NH3)5NO2]Cl(NO3) [Co(NH3)5ONO]Cl(NO3)

V < 0 (!)

but

V# > 0

Quantum yielddecreases (!) in the

elastically compressed parts of the crystals

h

0 10 20 30 40 50 60 70 801026

1028

1030

1032

1034

V, A

3

t, ч

0 1 2 3 4 5900

950

1000

V, A

3

P, ГПa

0 10 20 30 40 50 60 70 8010,410,510,610,710,810,911,011,111,2

a

c

a&c,

At, ч

0 1 2 3 4 510,010,110,210,310,410,510,610,710,8

a

ca&c,

A

P, ГПа

0 10 20 30 40 50 60 70 808,7

8,8

8,9

9,0

9,1

b, A

t, ч

0 1 2 3 4 58,6

8,7

8,8

8,9

9,0

b, A

P, ГПа

[Co(NH3)5ONO]Br2

Nitrito-nitro linkage thermal isomerization

Hydrostatic pressure

Effect of hydrostatic pressure on the linkage isomerization

[Co(NH3)5ONO]Br2 [Co(NH3)5NO2]Br2k1

k2

V > 0 (!)

but

V# < 0

Pressure accelerates

the reaction (!)

Introduction

Effects of the environment Response of the environment

Conclusions

“Реакция неотделима от среды,

в которой она протекает”

Н. Меншуткин, 1890 г.

“A reaction cannot be separated

from the medium”

N. Menschutkin, 1890 г.

Medium = Environment

• Solvent

• Cages of various types

• Crystalline environment in molecular crystals