Natta’s seeds with genetic modification Cristallography at University of Milano since the 1950‘s

Angelo Gavezzotti Dipartimento di Chimica, Università di Milano

Genealogy, 1

Piria 1814-1865 Cannizzaro 1826-1910 Ciamician 1857-1922 Cambi 1885-1968 Simonetta . 1920-1986

Piontelli, 1943

Natta, 1944-45 Genealogy, 2

Massimo Simonetta Graduated in Chemical Engineering at Politecnico (1946) “Assistente” at Politecnico, 1943-1954 He also held a degree in Industrial Chemistry (1943) and in Physics (1949), but mostly liked to be called ‘Ingegnere’ His mentors were Natta and Piontelli they (Natta) wanted him to build an electron diffraction machine Simonetta was an 'all thumbs' if ever there was one!

Pauling’s letter to Piontelli, 1950 "I shall be glad to have Mr.Simonetta working in our laboratory. I think...the best field for him to study... is the determination of the structure of organic gas molecules by the electron diffraction method" but that was not the case....

SIMONETTA's genetic modifiers… Pauling's court, 1950's

Pauling postdoctorals at CalTech, the 1950's: J.Dunitz, the small molecule X-ray gene M.Karplus, the theoretical chemistry gene among others: E.Heilbronner, K.Hedberg, K.Mislow...

Simonetta became Professor of Physical Chemistry

at University of Milano in 1955 (Polimi→Unimi)

Electrochemistry was in the hands of Giuseppe Bianchi Cambi was still alive and thundering well; referring to Bianchi's body (de)formation, he used to call out: "Shut up, you Rigoletto" (Cambi was not really politically correct)

Università-Politecnico: the continuing osmosis... I graduated in chemistry in 1968, one year later than this gentleman (Giuseppe Natta, whom I recall munching vitamin pills instead of going for lunch, to save time for studying)

Sergio Carrà Unimi→Polimi

Mario Farina Polimi→Unimi

...migration under differences in chemical potential

Simonetta's belongings, as of 1960-1970's

- Istituto di Chimica Fisica - Centro CNR per lo studio delle relazioni tra struttura

e reattività chimica (CSRSRC)

MOLECULES IN 3D join X-ray crystallography and theoretical chemistry

to study the relationships between structure and properties

we barely escaped this... but machines like this... ...produced films like this... .. ...and data went through machines like this

A.G. Graduation Thesis, 1968 probably first crystal structure solved in Italy by “direct” direct methods output of Bob Long's direct methods program*

*guess where the program came from? Ken Trueblood, associate of Verner Schomaker, Gates and Crellin Laboratories, CalTech...

The Syntex P1bar single-crystal X-ray diffractometer (1972, a spinoff of the Carl Djerassi hormone factory...!)

the way Simonetta managed science

the epic story of the [10]annulenes

basic theoretical idea: Roald Hoffmann, Cornell U. synthesis: Emanuel Vogel, Köln U.

bond topology: Richard Bader, McMaster U. X-ray group: some slaves at home

theoretical calculations: other slaves at home

R R' r(1-6), Å ____________________________ F F 2.27 H H 2.24 Me CN 1.71-1.85* Me Me 1.77-1.83 CN CN 1.54 *still the 'record' C-C bond length in the Cambridge Database

first class X-ray crystallography

Bader's bond topology analysis (AIM)

Gatti, Barzaghi and Simonetta, JACS 1984

Carlo Gatti post-doctored with Bader

H,H no bond F,F no bond

CN,CN CH3,CH3 CH3,CH3 1.54 1.77 1.83

Simonetta never touched a button or wrote a line of fortran, and one had to ask for his permission to use a diffractometer or even to consult a NASA Table of Integrals ! ... ...but none of us would have been able to put together Hoffmann, Vogel and Bader

*guess where the cryostat came from...? Sten Samson, CalTech...

R. Destro adapted to the P1bar diffractometer a 20-K, liquid helium cryostat

proton shift in citrinin by measuring the relative intensity of the proton peaks as a function of temperature, they were able to determine the reaction enthalpy doing X-ray thermodynamics!

Delta Fourier, 174 K Laplacian, 19±2 K 36,564 reflections measured!

work by Destro, Marsh, Merati, Roversi

further branching: from crystal structure to crystal forces Around 1970, a sub-group at Istituto di Chimica Fisica started a project forthe Born-von Kàrmàn treatment of lattice vibrations in organic crystals* *guess where Carlo Maria started his activity? CalTech, Gates and Crellin, with Dick Marsh

Carlo Maria Gramaccioli 1935-2013

phonon and optical dispersion curves required a titanic effort in conceiving, programming, and interpreting the calculations way was open to H, S, Cp by statistical mechanics (more X-ray thermodynamics!) prominent problem in the production of this paper: because of Pino Suffritti, Simonetta could not be the last author (who, in those times, was considered the most important one) Filippini, Gramaccioli, Simonetta, Suffritti, J.Chem.Phys. 1973

anthracene

things that happened in those days (1980's): we’re out of computer money!! sit down and write a review paper this is Simonetta (he said: "if they see my picture we will never get published“) this mafioso is your speaker

Vladimiro Scatturin (1922-2008) a school of inorganic X-ray crystallography metal carbonyl clusters

typical Scatturin handwork

Chemistry at Milano, the 1970’s the surroundings

Lamberto Malatesta, Vladimiro Scatturin, Massimo Simonetta: often arguing and quarreling ... Lamberto Malatesta (1912-2007)

...but working shoulder to shoulder, together with Raffaello Fusco, Luigi Canonica, Giuseppe Bianchi, they re-founded Chemistry in Milano after the war

people at Istituto di Chimica Fisica and Centro CNR, 1950-1980: X-ray: Bianchi, Casalone, Destro, Filippini, Gavezzotti, Gramaccioli, Mariani, Mugnoli, Pilati theoretical chemistry: Barzaghi, Cremaschi, Favini, Gamba, Gatti, Gianinetti, Morosi, Ortoleva, Polezzo, Raimondi, Tantardini others groups in LEED-Auger spectroscopy, EPR, Chemical kinetics, Industrial chemistry, etc. ..... sorry, too many to mention