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Phthalocyanines. Phthalocyanines:. From Molecular Structures to Solid-state Arrangements. Pigments. Charge-generating materials. Molecular properties  Solid-state properties PcCu b -PcCu is greenish blue e -PcCu is reddish blue.

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from molecular structures to solid state arrangements

Phthalocyanines

Phthalocyanines:

From Molecular Structures to Solid-state Arrangements

Pigments

Charge-generating

materials

Molecular properties  Solid-state properties PcCu b-PcCu is greenish bluee-PcCu is reddish blue

Classification of Phthalocyanine Molecular Structures

Arrangement of the Phthalocyanine Units in Solid-state

Start: Basic information about Phthalocyanine Molecular Structures

Structure-Property Relationships

Dr. Michael Klaus ENGEL (michael-engel@ma.dic.co.jp)

Dainippon Ink & Chemicals, Inc.

Central Research Laboratories; Sakura-shi, Japan

ICPP-3, New Orleans, July 12, 2004

molecular structures basics

X=CH: Tetrabenzoporphyrin: TBPH2

1) 139.0 pm

2) 249.5 pm; 127.9°

3) 295.5 pm

4) 688.6 pm

X=N: Phthalocyanine: PcCo

1) 131.7 pm

2) 229.7 pm; 121.5°

3) 269.8 pm

4) 670.5 pm

Molecular Structures: Basics

  • Most of the metallic elements and semimetals can be coordinated in the
  • center of the macrocycle.
  • Molecular structure is influenced by
  • - the size of the central atom M,
  • - the oxidation state of the central atom M.
  • Two kinds of molecular axes:
  • - bridging-nitrogen molecular axis (Nbr)
  • isoindole-nitrogen molecular axis (Ni)

ICPP-3, New Orleans, July 12, 2004

molecular structures basics1

Molecular Structures: Basics

ICPP-3, New Orleans, July 12, 2004

molecular structures monomers

Molecular Structures: Monomers

ICPP-3, New Orleans, July 12, 2004

molecular structures dimers

Molecular Structures: Dimers

ICPP-3, New Orleans, July 12, 2004

increased possibilities of interactions

Aromatic hydrocarbons:

Interaction between aromatic macrocycles: p-p interactions and H-p interactions

Increased possibilities of interactions

Phthalocyanines additional interaction

possibilities due to the presence of

heteroatoms.

Hydrogen atoms  electronegative atoms

Nitrogen atoms  hydrogen atoms

 axial ligands

 central atoms

Central atoms and axial ligands

 central atoms

 axial ligands

 nitrogen atoms

ICPP-3, New Orleans, July 12, 2004

arrangements group cn4 pcm

Arrangements: Group CN4 (PcM)

4 Basic overlap geometries

a-PcPt

b-PcH2

a-PcCu

x1-PcH2

the big confusion

overlap along Ni molecular axis

overlap along Nbr molecular axis

intermolecular bonding between Nbr and center stabilizes b-polymorphs

ICPP-3, New Orleans, July 12, 2004

arrangements group cn4 pcm1

Orientation of phthalocyanines in neighboring columns

Arrangements: Group CN4 (PcM)

a-PcPt

a-PcCu

2.7044 Å

Herringbone stacking

b-PcH2

x1-PcH2

2.6465 Å

S2 screw axis

Intercolumnar hydrogen-bonding

intercolumnar distances

N…H > 3.2 Å

much weaker bonding

ICPP-3, New Orleans, July 12, 2004

arrangements group cn4 pcm2

a-PcPt

g-PcPt

(Nbr)

2.6134 Å

b-PcH2

3.0143 Å

3.0499 Å

Arrangements: Group CN4 (PcM)

(Ni)

2.8408 Å

x1-PcH2

a-PcCu

x2-PcH2

x1-PcH2

ICPP-3, New Orleans, July 12, 2004

arrangements group cn6tr pcmx 2

Arrangements: Group CN6tr (PcMX2)

spatial need of axial ligands

Intermol. hydrogen bonding

+ repulsive interaction

much smaller in CN6tr

overlap in CN4

x1-PcH2

PcCoCl2

PcSnI2

PcSnI2

ICPP-3, New Orleans, July 12, 2004

arrangements group cn6tr pcmx 21

Network structure

view along the column axes

Arrangements: Group CN6tr (PcMX2)

2.568 Å

a-PcGe(OH)2

Intercolumnar 

hydrogen bonding

  • Network structure

view along the column axes

b-PcGe(OH)2

x1-PcH2

2.592 Å

Intercolumnar 

hydrogen bonding

ICPP-3, New Orleans, July 12, 2004

molecular structures group cn5 pcmx

Why do some phthalocyanines have a saucer-shaped macrocycle ?

Molecular Structures: Group CN5 (PcMX)

convex face

concave face

  • 2 different faces
  • each face leads to a different arrangement

ICPP-3, New Orleans, July 12, 2004

arrangements group cn5 pcmx

convex

concave

Arrangements: Group CN5 (PcMX)

Ni

Nbr

no shift

sheet-type (or brickstone) arrangement

columnar (slipped-stacked) arrangements

layer-type arrangements

ICPP-3, New Orleans, July 12, 2004

arrangements group cn5 pcmx1

molecular lego

Arrangements: Group CN5 (PcMX)

 PcGaCl

+

Ni

+

 PcAlCl

Nbr

+

 PcZnCl

no shift

layer-type convex

concave

ICPP-3, New Orleans, July 12, 2004

hydrogen bonding

Hydrogen bonding

not parallel

I-PcTiO

orientation through hydrogen-bonding

ca. 3.5 Å hydrogen bonding

parallel

2.746 Å

PcSn

2.736 Å

PcNbCl2

PcSnCl2

flattening through

repulsive interaction

molecular deformation through hydrogen-bonding

ICPP-3, New Orleans, July 12, 2004

mol structures group cn8bis pc 2 m

bisphthalocyanines

Mol. Structures: Group CN8bis (Pc2M)

until now: defined by

staggeringanglea

but: angle depends on

which units are used

angle corresponds to

crystal structure

staggering angle is not a

molecular property

ICPP-3, New Orleans, July 12, 2004

arrangements group cn8bis pc 2 m

[Pc2Lu]

[CH2Cl2]

Arrangements: Group CN8bis (Pc2M)

2

12

a-Pc2Er

1

2

Pc2Ce

A1

A

1

A2

b-Pc2Pr

ICPP-3, New Orleans, July 12, 2004

arrangements group cn8bis pc 2 m1

[Pc2Lu][CH2Cl2] (12)

Pc2Ce (A2)

b-Pc2Pr (A1)

Arrangements: Group CN8bis (Pc2M)

ICPP-3, New Orleans, July 12, 2004

final remarks

Final remarks

  • The central atom together with axial ligands controls
  • molecular structure and arrangement in the solid-state.
  • Phthalocyanines like to slip-stack.
  • Hydrogen-bonding is a major force.
  • Molecular properties (deformation) depend on the crystal arrangement
  • calculation of crystal structures need to use non-rigid molecules

This talk covered only pure materials, no mixtures. Co-crystallizing

materials (impurities, solvents) can stronglyinfluence the crystal

structure.

Further reading:

M.K. Engel, J. Porph. Phthalocyanine, in preparation

M.K. Engel, in "The Porphyrin Handbook",

Vol. 20, 2003, 1-246

P. Erk et al., CrystEngComm, 2004, accepted

ICPP-3, New Orleans, July 12, 2004

thank you

Thank you

To you for listening.

To Prof. Heiner Homborg for many discussions and giving me access

to his unpublished crystal structures.

To Dr. Peter Erk for preprints and unpublished structures.

To Prof. Bob Scheidt for his work in porphyrin crystal structures which

gave me many ideas for phthalocyanine crystal structures.

To Dainippon Ink and Chemicals for having interest in my phthalocyanine

research and allowing me to participate at this conference.

Michael Klaus Engel

michael-engel@ma.dic.co.jp

http://phthalo.mkengel.de/pcrev.htm

ICPP-3, New Orleans, July 12, 2004